Acetylene derivatives and crop protection agents containing them

ABSTRACT

Acetylene derivatives of the general formula I ##STR1## where U, V and W are hydrogen, halogen, nitro, cyano, alkyl or alkoxy, 
     A is alkylidene, alkoxymethylidene, alkylthiomethylidene or alkoximino, 
     B is OH, alkoxy or alkylamino and 
     R is hydrogen, halogen, cyano, CF 3 , alkyl, cycloalkyl, haloalkyl, aryl, alkenyl, alkynyl, heterocyclyl, hetaryl, arylalkyl, arylalkenyl, arylethynyl, hetaryl-C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy-C 1  -C 4  -alkyl, aryloxyalkyl, hetaryloxyalkyl, arylamino-alkyl, arylthiomethyl, hetarylthiomethyl, C(O)R 1 , C(O)NR 2  R 3 , C(S)NR 4  R 5 , C(O)SR 6 , C(S)OR 7 , C(S)SR 8 , CH(OH)R 9 , CH(OR 10 )R 11 , SiR 12  R 13  R 14 , SnR 15  R 16  R 17 , C(OR)R 18  or C(═N--OR 19 )R 20  and 
     R 1  -R 17 , R 19  and R 20  are hydrogen, alkyl, aryl, hetaryl, arylalkyl or hetarylalkyl and R 18  is OH, C 1  -C 4  -alkoxy or aryl-C 1  -C 4  -alkoxy, and fungicides containing these compounds.

This is a division, of application Ser. No. 08/099,693 filed on Jul. 30, 1993, allowed.

The present invention relates to novel acetylene derivatives and a method for controlling pests, in particular fungi, insects, nematodes and spider mites, with these compounds.

It is known that individual acetylene derivatives (European Patents 178,826, 244,077, 253,213, 280,185 and 477,631, have fungicidal or insecticidal activity. However, their activity is unsatisfactory.

We have found, surprisingly, that the novel acetylene derivatives of the general formula I ##STR2## where U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,

A is C₁ -C₄ -alkylidene, C₁ -C₄ -alkoxymethylidene, C₁ -C₄ -alkylthiomethylidene or C₁ -C₄ -alkoximino,

B is OH, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, and

R is hydrogen, halogen, cyano, CF₃, straight-chain or branched C₁ -C₁₀ -alkyl, C₃ -C₆ -cycloalkyl, unsubstituted or substituted aryl, halo-C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl, C₂ -C₄ -alkynyl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted hetaryl, unsubstituted or substituted aryl-C₁ -C₄ -alkyl, unsubstituted or substituted aryl-C₂ -C₄ -alkenyl, unsubstituted or substituted arylethynyl, unsubstituted or substituted hetaryl-C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, unsubstituted or substituted aryloxy-C₁ -C₄ -alkyl, unsubstituted or substituted hetaryloxy-C₁ -C₄ -alkyl, unsubstituted or substituted arylamino-C₁ -C₄ -alkyl, unsubstituted or substituted arylthiomethyl, unsubstituted or substituted hetarylthiomethyl, C(O)R¹, C(O)NR₂ R³, C(S)NR⁴ R⁵, C(O)SR⁶, C(S)OR⁷, C(S)SR⁸, CH(OH)R⁹, CH(OR¹⁰)R¹¹, SiR¹² R¹³ R¹⁴, SnR¹⁵ R¹⁶ R¹⁷, C(O)R¹⁸ or C(═N--OR¹⁹)R²⁰ and

R¹ -R¹⁷, R¹⁹ and R²⁰ are identical or different and are each hydrogen, C₁ -C₄ -alkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl, unsubstituted or substituted arylalkyl or unsubstituted or substituted hetarylalkyl,

R¹⁸ is OH, C₁ -C₄ -alkoxy or unsubstituted or substituted aryl-C₁ -C₄ -alkoxy, the term "unsubstituted or substituted" denoting, in addition to hydrogen, the substitutents halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy, benzyl, benzyloxy, hetaryl, hetaryloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄ -dialkylamino, CO₂ Me, CO₂ Et, formyl and acyl, Me being methyl, Et being ethyl and the expression hetaryl being an aromatic five-membered or six-membered heterocyclic structure, with the exception of the following individual compounds of the general formula I where

A is CHOCH₃, B is OCH₃ and R is phenyl,

A is CHSCH₃, B is OCH₃ and R is phenyl,

A is CHCH₃, B is OCH₃ and R is phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,

A is NOCH₃, B is OCH₃ and R is phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,

A is NOCH₃, B is NHCH₃ or R is CH₃ or phenyl,

A is CHOCH₃, B is NHCH₃ and R is CH₃ or phenyl and

A is CHSCH₃, B is NHCH₃ and R is phenyl, have excellent fungicidal, insecticidal, nematicidal and acaricidal activity.

The fungicidal and insecticidal activity is preferred.

The radicals stated for the general formula I may have, for example, the following meanings:

U, V and W may each be hydrogen, halogen (eg. fluorine, chlorine, bromine or iodine), methyl or methoxy,

A may be C₁ -C₄ -alkylidene (eg. methylidene, ethylidene, n-propylidene, isopropylidene, n-butylidene, isobutylidene, sec-butylidene or tert-butylidene), C₁ -C₄ -alkoxymethylidene (eg. methoxy-, ethoxy-, n-propoxy-, isopropoxy-, n-butoxy-, isobutoxy-, sec-butoxy- or tert-butoxymethylidene), C₁ -C₄ -alkylthiomethylidene (eg. methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, sec-butyl- or tert-butylthiomethylidene), C₁ -C₄ -alkoximino (eg. methoximino, ethoximino, n-propoximino, isopropoximino, n-butoximino, isobutoximino, secbutoximino or tert-butoximino),

B may be OH, C₁ -C₄ -alkoxy (eg. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tertbutoxy) or C₁ -C₄ -alkylamine (eg. methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine or tert-butylamine), and

R is hydrogen, halogen (fluorine, chlorine, bromine or iodine), cyano, CF₃, straight-chain or branched C₁ -C₁₀ -alkyl (eg. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl or n-decyl), C₃ -C₆ -cycloalkyl (eg. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), unsubstituted or substituted aryl (eg. phenyl, naphthyl or anthryl), halo-C₁ -C₄ -alkyl (eg. bromomethyl, chloromethyl, iodomethyl or CF₃ -methyl), C₂ -C₆ -alkenyl (eg. vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 3-methyl-2-butenyl or 2-methyl-2-penten-5-yl), C₂ -C₄ -alkynyl (eg. ethynyl or 1-propynyl), unsubstituted or substituted heterocyclyl (eg. oxiranyl, 1-aziridinyl, 1-azetidinyl, 1-pyrrolidinyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 1-piperidinyl, 1-morpholinyl, 1-piperazinyl, 1,3-dioxanyl, 3-tetrahydrothiopyranyl), unsubstituted or substituted hetaryl (eg. pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3-furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl, 2-benzothiazolyl), unsubstituted or substituted aryl-C₂ -C₄ -alkyl (eg. benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 2-methyl-3-phenylpropyl, 2-methyl-2-phenylpropyl or 4-phenylbutyl), unsubstituted or substituted aryl-C₁ -C₄ -alkenyl (eg. phenyl-1-ethenyl, 2-phenyl-1-propenyl, 2,2-diphenylethenyl, 1-phenyl-1-propen-2-yl or 1-phenyl-1-ethenyl), unsubstituted or substituted arylethynyl (eg. phenylethynyl), unsubstituted or substituted hetaryl-C₁ -C₄ -alkyl (eg. pyridylmethyl or 3-pyridylmethyl), C₁ -C₄ -alkoxy-C₁ -C₄ alkyl (eg. methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl, tert-butoxymethyl, 2-methoxyprop-2-yl, 2-ethoxyprop-2-yl, 2-n-propoxyprop-2-yl, isopropoxyprop-2-yl, 2-n-butoxyprop-2-yl, isobutoxyprop-2-yl, sec-butoxyprop-2-yl or tert-butoxyprop-2-yl), unsubstituted or substituted aryloxy-C₁ -C₄ -alkyl (eg. phenoxymethyl), unsubstituted or substituted hetaryloxy-C₁ -C₄ -alkyl (eg. 2-thienyloxymethyl), unsubstituted or substituted arylamino-C₁ -C₄ -alkyl (eg. N-(phenylamino)-methyl), C(O)R¹ (eg. C(O)CH₃, C(O)CH₂ CH₃ or C(O)phenyl), C(O)NR² R³ (eg. C(O)NH₂, C(O)NHCH₃), C(S)NR² R³ (eg. C(S)NH₂ or C(S)NHCH₃), C(O)SR⁶ (eg. C(O)SCH₃ or C(O)SCH₂ C₆ H₅), C(O)OR⁷ (eg. CO₂ CH₃ or CO₂ CH₂ C₆ H₅), C(S)SR⁸ (eg. CS₂ CH₃), CH(OH)R⁹ (eg. H(OH)C₆ H₅), CH(OR¹⁰)R¹¹ (eg. CH(OCH₃)C₆ H₅), SiR¹² R¹³ R¹⁴ (eg. SiMe₃) SnR¹⁵ R¹⁶ R¹⁷ (eg. SnMe₃), C(O)R¹⁸ (eg. CO₂ Me, CO₂ CH₂ C₆ H₅) or C(═N--OR¹⁹)R²⁰ (eg. C(NOMe)C₆ H₅).

R¹ -R¹⁷, R¹⁹ and R²⁰ are, for example, hydrogen C₁ -C₄ -alkyl (eg. methyl, ethyl, n- and isopropyl, n-, iso-, sec- and tert-butyl), unsubstituted or substituted aryl (eg. 2-chlorophenyl, 3,5-dimethylphenyl and 1-methyl-2-naphthyl), unsubstituted or substituted hetaryl (eg. 6-chloro-2-pyrridyl, 4-pyrimidinyl, 2-furyl and 6-methylbenzthiazol-2-yl), unsubstituted or substituted arylalkyl (eg. 2-chlorobenzyl and 3,5-dichlorobenzyl) and unsubstituted or substituted hetarylalkyl (eg. 2-furylmethyl and 6-methyl-2-pyridylmethyl) and

R¹⁸ is, for example, OH, C₁ -C₄ -alkoxy (eg. methoxy and ethoxy) and unsubstituted or substituted aryl-C₁ -C₄ -alkoxy (eg. 2-chlorobenzyloxy).

The radicals defined above as unsubstituted or substituted contain as substituents, apart from hydrogen, for example fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, tert-butoxy, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, methoximinomethyl, ethoximinomethyl, n-propoximinomethyl, n-butoximinomethyl, n-pentoximinomethyl, n-hexyloximinomethyl, allyloximinomethyl, benzyloximinomethyl, isopropoximinomethyl, isobutoximinomethyl, tert-butoximinomethyl, methylimino-1-ethyl, ethoximino-1-ethyl, n-propoximino-1-ethyl, n-butoximino-1-ethyl, n-pentoximino-1-ethyl, n-hexoximino-1-ethyl, allyloximino-1-ethyl, benzyloximino-1-ethyl, phenyl, phenoxy, benzyl, benzyloxy, imidazol-1-yl, piperazin-1-yl, 4-morpholinyl, piperidin-1-yl, pyridyl-2-oxy, cyclopropyl, cyclohexyl, oxiranyl, 1,3-dioxan-2-yl, 1,3-dioxan-2-yl, tetrahydropyran-2-yloxy, dimethylamino, diethylamino, CO₂ Me, CO₂ Et, formyl or acyl, Me being methyl and Et being ethyl.

The compounds of the general formula I ##STR3## where U, V and W are each hydrogen,

A is ethylidene, methoxymethylidene or methoximino,

B is methoxy or methylamine and

R has the abovementioned meanings, are preferred.

Owing to the C═C or C═N double bonds, the novel compounds of the general formula I maybe obtained in the preparation as E/Z isomer mixtures. These can be separated into the individual components in a conventional manner, for example by crystallization or chromatography. Both the individual isomeric compounds and mixtures thereof form subjects of the invention and can be used as pesticides.

The compounds of the general formula I as claimed in claim 1 are prepared, for example, as described in the following schemes:

The novel compounds of the general formula I can be prepared by reacting, for example, an o-bromo compound 2 with a terminal acetylene derivative 3 in the presence of a transition metal catalyst, preferably a palladium compound, eg. Pd(PPh₃)₄, PdCl₂ or Pd(OAc)₂, in the presence of triphenylphosphine and in the presence of a base, for example an N-alkylamine, such as triethylamine, and in the presence or absence of a solvent or diluent, eg. dimethylformamide or acetonitrile (cf. for example L. Brandsma et al., Synth. Comm. 20(1990), 1889 and W. B. Austin et al., J. Org. Chem. 46(1981), 2280). ##STR4##

A, B, R, U, V and W have the meanings stated in claim 1.

Alternatively, the compounds of the general formula 1 are obtained by reacting the o-bromo-α-keto acid derivatives 4 with the acetylenes of the formula 3 (conditions similar to Scheme 1) ##STR5## and then reacting the resulting α-ketocarboxylic acid derivatives 5 a) for example in a wittig or a Wittig-Horner-Emmons reaction with a phosphonium ylide 6 or with a phosphonic acid derivative 7 (Scheme 3) to give the novel compounds of the formula 1, where B, U, V, W and R have the meanings stated in claim 1 and A is CH-alkyl, CH-alkoxy or CH-thioalkyl (cf. for example C. Ferri, Reaktionen der organischen Synthese, Thieme Verlag, Stuttgart, page 354 et seq., 1978), or

R'=CH₃, M.sup.⊕ =alkali metal ion

Scheme 3

b) with an O-alkylhydroxylamine 8, in the presence or absence of an acid, eg. hydrochloric acid, or of a ##STR6## bse, eg. K₂ CO₃, to give the novel compounds of the formula 1 in which B, U, V, W, R and R⁴ have the meanings stated in claim 1 (cf. for example European Patent 253,213). ##STR7##

The novel compounds of the general formula 1 can also be prepared by reacting the terminal acetylenes 9, by a transition metal (TM)-catalyzed coupling, with the halides 10, preferably with the bromides (X=Br), or the iodides (X=I) in the presence of a catalyst, eg. PdCl₂, Pd(OAc)₂ or Pd(PPh₃)₄, and of a base, such as triethylamine (cf. for example P. C. Vollhardt, Angew. Chem. 98 (1986), 268 and H. Yamanaka, Synthesis (1983), 312).

Scheme 5

A, B, R, U, V and W have the meanings stated in claim 1.

In an alternative procedure, the α-keto acid derivatives of the terminal acetylenes 11 can be converted with the halides 10 under transition metal ##STR8## (TM)-catalysis into the derivatives 5, and the latter can be converted as described above into the novel compounds of the formula 1. ##STR9##

In a further possible method for the preparation of the compounds of the general formula 1, the acetylene group in formula 12 is first produced by a known method (cf. for example Houben-Weyl, Vol. V/2a, page 33 et seq. (Viehe) or see Schemes 1+2) ##STR10## and the group Y is then converted into the group ##STR11##

Schemes 7-9 are intended to illustrate this. The ketocarboxylic esters 17 can be prepared starting from the o-bromobenzaldehydes 13. ##STR12##

The o-bromobenzaldehydes 12 can be reacted with the terminal acetylenes 3 under transition metal catalysis to give the aldehydes 14 (cf. W. B. Austin, J. Org. Chem. 46 (1981), 2280).

The cyanohydrins 15 are obtained from the aldehydes 14 by reaction with a metal cyanide, such as NaCN or KCN, in the presence of an acid, eg. hydrochloric acid (cf. for example Organikum, 16th Edition, page 445 (1986)).

The mandelic acid derivatives 16 can be prepared from the cyanohydrins 15 via a Pinner reaction (cf., for example, Org. Synth. Coll. 4(1963), 58).

Oxidation of the mandelic acid derivatives 16, for example with a chromium compound, such as chromium trioxide, with sodium hypochlorite or with TEMPO gives the α-ketoesters 17 (cf. for example Houben-Weyl, Vol. 4/1b, pages 425-464 (1975); TEMPO=tetramethylpiperidin-1-oxyl ).

The novel compounds of the formula 1a, in which A, U, V, W and R have the meanings stated in claim 1 and B is CO₂ Me, can be prepared from the ketoesters 17 as shown in Schemes 3 and 4. The α-ketocarboxylic esters 17 can be synthesized starting from the halogen derivatives 18, by Grignard reaction with oxalic acid compounds 19 similarly to Scheme 8 (cf., for example, J. S. Nimitz, J. Org. Chem. 46 (1981), 211). ##STR13##

In a further possible method, carboxylic acids 20 are converted via the stage of the acyl chlorides into the cyanides 21 and the latter are converted into the ketoesters 17 by a Pinner reaction. ##STR14## (cf. for example Organikum, 16th Edition, 423 et seq. (1986) and Angew. Chem. 94 (1982), 1).

The novel compounds of the formula 1 where A, X, Y, Z and R have the meanings stated in claim 1 and B is hydroxyl or alkylamino can be prepared from the carboxylic ester derivatives 1a. ##STR15##

The carboxylic acids 22 are obtained by hydrolysis by known methods (cf. Organikum, 16th Edition, page 415 et seq. and page 622 (1986)).

They can be converted into the acyl chlorides 23 (cf. Organikum, 16th Edition, page 423 et seq. (1986)).

The amides 24 are either obtained from these in a conventional manner (Organikum, 16th Edition, page 412 (1986)) or alternatively from the carboxylic esters 1a directly by aminolysis with amines.

However, the novel compounds of the general formula I can also be prepared by converting a suitably substituted styryl compound 25 in a conventional manner into the corresponding acetylene derivative 1. ##STR16##

Where X is H and Y is halogen or X is halogen and Y is H, the reaction is carried out in the presence of a base, eg. sodium hydride, potassium hydroxide, Triton B or n-butyllithium (cf. for example H. Zimmer et al., Chimia 28 (1974), page 656 et seq.) (Triton B=2-benzyltrimethylammonium hydroxide).

Where X and Y are each halogen, the cleavage can be carried out with zinc (cf. for example H. G. Viehe, Chemistry of Acetylenes, Marcel Dekker, New York, 1969, page 134 et seq.).

The Examples which follow illustrate the preparation of the compounds.

EXAMPLES Example 1

Preparation of methyl 2-ethynylphenylglyoxylate O-methyloxime (compound 1, Table 2)

33.3 g (0.35 mol) of trimethylsilylacetylene, 3.8 g of palladium(II) acetate, 3.2 g of copper(I) iodide and 8.9 g of triphenylphosphine are added to a solution of 55.4 g (0.23 mol) of methyl 2-bromophenylglyoxylate in 415 ml of triethylamine, and nitrogen is then passed through the solution for 30 minutes. The reaction mixture is then heated at 90° C. for 45 minutes, is allowed to cool and is filtered off. The filtrate is evaporated down, the residue is taken up in ethyl acetate and the solution is washed with water. The organic phase is dried and evaporated form. 56.8 g of α-ketoester remain as a black oil.

The crude product prepared in this manner is dissolved in 50 ml of methanol, 38.9 g (0.37 mol) of O-methylhydroxylamine hydrochloride ale added and heating is carried out for 15 minutes at 60° C. The mixture is evaporated down, the residue is taken up in ethyl acetate and the solution is washed with water. The organic phase is dried and evaporated down. 52.4 g of compound No. 2 (Table 2) remain as a black oil. ¹ H-NMR (CDCl₃ /TMS): δ=0.22 (s, 9H, SiMe₃); 3.86; 4.06 (s, 3H, OCH₃); 7.25-7.61 ppm (m, 4H, aryl).

The trimethylsilylacetylene compound prepared in this manner is dissolved in 320 ml of methanol and stirred together with 3.2 g of potassium carbonate for 1 hour at room temperature (20° C.). The mixture is then evaporated down, the residue is taken up in methylene chloride and the solution is washed with 10% strength sodium bicarbonate solution. The organic phase is dried and evaporated down. 36 g (72%, based on methyl 2-bromophenylglyoxylate) of compound 1 (Table 2) remain as a black solid. ¹ H-NMR (CDCl₃ /TMS): δ=3.17 (s, 3H, .tbd.C--H); 3.87; 4.07 (s 3H, OCH₃); 7.27-7.60 ppm (m, 4H, aryl).

Example 2

a) Preparation of methyl 2-(2-methylphenyl)-ethynylphenylglyoxylate O-methyloxime (European Patent 253,213, No. 136)

300 mg of palladium(II) acetate, 1.5 g of triphenylphosphine and 100 mg of copper(I) iodide and 11 g (0.095 mol) of 2-methylphenylacetylene are added to a solution of 10 g (0.041 mol) of methyl 2-bromophenylglyoxylate in 50 ml of triethylamine. Nitrogen is passed through the solution for 30 minutes, after which the solution is heated for 3 hours at 80° C. After cooling, methylene chloride is added and the solution is washed with water. The organic phase is dried and evaporated down. 16.5 g of methyl 2-(2-methylphenyl)-ethynylphenylglyoxylate remain as a black oil. ¹ H-NMR (CDCl₃ /TMS): δ=2.53 (s, 3H, CH₃); 3.81 (s, 3H, OCH₃); 7.13-7.88 ppm (m, 8H, aryl).

74 g (0.089 mol) of methoxyamine hydrochloride are added to the ketoester obtained in this manner, in 20 ml of methanol, and refluxing is carried out for 1.5 hours. The mixture is evaporated down, the residue is taken up in ethyl acetate, the solution is washed with water and the organic phase is dried and evaporated down. 9.5 g of the product remain as a black oil, which can be recrystallized from methanol. The above mentioned compound is obtained in this manner as a colorless solid having a melting point of 92°-96° C. ¹ H-NMR (CDCl₃ /TMS): δ=2.46 (s, 3H, CH₃); 3.83; 4.07 (s, 3H, OCH₃); 7.12-7.63 ppm (m, 8H, aryl).

b) N-Methyl-2-(2-methylphenylethynyl)-phenylglyoxylamide O-methyloxime (compound 32, Table 4)

2 g (7 mmol) of the compound prepared in Example 2a are added to 50 ml of a 40% strength methylamine solution and the mixture is stirred overnight at room temperature. Extraction with ether, drying and evaporation are then carried out. 0.9 g (42%) of compound 32 (Table 4) remains as a pale yellow solid of melting point 128°-129° C. ¹ H-NMR (CDCl₃ /TMS): δ=2.43 (s, 3H, CH₃); 2.91 (d, 3H, NCH₃); 3.96 (s, 3H, OCH₃); 6.75 (br, 1H, NH); 7.14-7.63 ppm (m, 8H, aryl).

Example 3

Methyl 2-(2-(3-chloro)thienylethynyl)-phenylglyoxylate O-methyloxime (compound 178, Table 2)

100 mg of palladium(II) acetate, 87 mg of copper(I) iodide and 240 mg of triphenylphosphine are added to a solution of 2 g (0.009 mol) of methyl 2-ethynylphenylglyoxylate O-methyl oxime (Example 1) and 3.6 g (0.018 mol) of 2-bromo-3-chlorothiophene in 100 ml of triethylamine. Nitrogen is passed through the solution for 30 minutes, after which the solution is heated for 1 hour at 90° C. The solid formed is filtered off and the filtrate is evaporated down. The residue is taken up in ethyl acetate, the solution is washed with water and the organic phase is dried and evaporated down.

The remaining crude product is chromatographed over silica gel using hexane methyl tert-butyl ether.

As the first fraction, 700 mg (23%) of compound 178 (Table 2) are obtained in the form of a brown oil. ¹ H-NMR (CDCl₃ /TMS): δ=3.88; 4.09 (s, 3H, OCH₃); 6.93 (d, 1H, ═CH); 7.25 (d, 1H, ═CH); 7.27-7.66 ppm (m, 4H, aryl).

500 mg (13%) of dimeric starting material are obtained as the second fraction (compound 162, Table 2). ¹ H-NMR (CDCl₃ /TMS): δ=3.91; 4.09 (s, 3H, OCH₃); 7.27-7.61 ppm (m, 4H, aryl).

2. Method 1:

Methyl α- 2-(phenylethynyl)-phenyl!-β-methylacrylate European Patent 280,185, No. 136!

300 mg of palladium(II) acetate, 1.5 g of triphenylphosphine and 100 mg of copper(I) iodide are added to a solution of 10 g (0.041 mol) of methyl 2-bromophenylglyoxylate and 6.3 g (0.061 mol) of phenylacetylene in 50 ml of triethylamine. Nitrogen is passed through the solution for 30 minutes, after which the solution is heated for 90 minutes at 90° C. It is then evaporated down and the residue is taken up in methylene chloride. The solution is washed with water, dried and evaporated down. The remaining residue is chromatographed over silica gel using hexane/methyl tert-butyl ether. 5.5 g of α-ketoester remain as a brown oil after evaporating down. ¹ H-NMR (CDCl₃ /TMS): δ=2.82 (s, 3H, CH₃); 7.36-7.88 ppm (m, 9H, aryl).

2.4 g (0.021 mol) of potassium tert-butylate are added at 5° C. to a solution of 8.7 g (0.021 mol) of ethyltriphenylphosphonium iodide in 60 ml of dry tetrahydrofuran. Stirring is carried out for 1 hour at this temperature, after which a solution of 5.5 g (0.021 mol) of α-ketoester (see above) in 20 ml of tetrahydrofuran is added dropwise at 5° C. and stirring is continued for 3 hours at room temperature. The reaction batch is poured onto water and extracted with methylene chloride, and the organic phase is dried and evaporated down. Chromatography over silica gel using hexane/methyl tert-butyl ether gives 1.2 g of the compound European Patent 280,185, No. 136! as a brown oil in the form of an E/Z mixture. ¹ H-NMR (CDCl₃ /TMS): δ=1.74 (d, 3H, CH₃ -isomer A); 2.22 (d, 3H, CH₃ -isomer B); 3.70; 3.71 (s, 3H, CH₃ -isomer A, B); 6.38 (q, 1H, CH); 7.17-7.61 ppm (m, 9H, aryl).

Example 4

Preparation of methyl α-{2- 2-(4-chlorophenyl)-isoxazol-5-ylethynyl!-phenyl}-β-methoxyacrylate (compound 195, Table 1)

0.8 g of methyl α-{2- 2-chloro-2-(3- 4-chloro-phenyl!-isoxazol-5-yl)-ethenyl!-phenyl}-β-methoxyacrylate (European Patent 378,755) is dissolved in 10 ml of anhydrous dimethyl sulfoxide, and a pinch of sodium hydride is added. Stirring is carried out overnight at room temperature, and the mixture is poured onto ice water and extracted three times with dichloromethane. The combined organic phases are washed three times with water, dried over sodium sulfate and then evaporated down in a rotary evaporator. The residue is triturated with diisopropyl ether. 0.3 g of the title compound is obtained as colorless crystals of melting point 107°-110° C. ¹ H-NMR (CDCl₃ /TMS): δ=3.7 (s, 3H); 3.85 (s, 3H); 6.7 (s, 1H); 7.2-7.8 (m, 9H).

Example 5

Preparation of 2-ethynylphenylglyoxylic acid-N-methylamide-O-methyloxime

1 g (4.6 mmol) of the acetylene compound prepared in Example 1 is added to 20 ml of a 40% strength methylamine solution, and the mixture is stirred for 45 minutes at 40°-50° C. The solution is extracted with methyl tert-butyl ether, dried and evaporated down. 700 mg (70%) of the compound remain as a colorless solid.

¹ H-NMR (CDCl₃ /TMS): δ=2.99 (d, 2H, NCH₃); 3.13 (s, 1H, .tbd.C--H), 3.98 (s, 3H, OCH₃), 6.80 (br, 1H, NH); 7.21-7.58 ppm (m, 4H).

Example 6

Preparation of methyl 2-benzoyl-ethynylphenylglyoxylate O-methyloxime (compound 26, Table 6)

Under a nitrogen blanket and at 90° C., 2 g (9.2 mmol) of the acetylene derivative from Example 1 is added to a mixture of 50 mg of copper(II) chloride, 110 mg of palladium(II) acetate, 380 mg of triphenylphosphine and 2.6 g (18.4 mmol) of benzoyl chloride in 100 ml of triethylamine. After 30 minutes, the mixture is allowed to cool and the solid is filtered off. The filtrate is evaporaed down, and the residue is taken up in methyl tert-butyl ether, washed with water, dried and evaporated down. The residue is stirred with diethyl ether and the precipitated pale brown solid is filtered off. 2.0 g (68%) of compound 26, Table 6, remain. Mp. 89°-94° C.

Example 7

Preparation of methyl 2-(methoxyiminobenzoyl)ethynylphenylglyoxylate O-methyloxime (compound 10, Table 9).

A mixture of 1.5 g (4.7 mmol) of compound 26 from Table 6 (from Example 6) and 2.6 g of O-methylhydroxylamine hydrochloride in 5 ml of methanol is heated for 90 min at 60° C. The mixture is evaporated down and the residue is taken up in methyl tert-butyl ether and washed with water, followed by drying and evaporating down. The residue is chromatographed on silica gel using mixtures of methyl tert-butyl ether and hexane. 1.1 g (67%) of compound 10 from Table 9 remain as a yellow oil (isomer mixture).

₁ H-NMR (CDCl₃ /TMS): δ=3.81; 4.04; 4.12 (3H, OCH₃); 7.28-7.88 ppm (9H).

                  TABLE 1                                                          ______________________________________                                          ##STR17##                                                                                                 phys. data                                                                     (m.p.  °C.!);                                                           IR  cm.sup.-1 !;                                   No.  R                      .sup.1 H-NMR  δ scale!                       ______________________________________                                         1    H                                                                         2    SiMe.sub.3                                                                3    S.sub.n Me.sub.3                                                          4    I                                                                         5    CN                                                                        6    CH.sub.3                                                                  7    CH.sub.2 CH.sub.3                                                         8    n-C.sub.3 H.sub.7                                                         9    i-C.sub.3 H.sub.7                                                         10   n-C.sub.4 H.sub.9                                                         11   i-C.sub.4 H.sub.9                                                         12   s-C.sub.4 H.sub.9                                                         13   t-C.sub.4 H.sub.9                                                         14   n-C.sub.5 H.sub.11                                                        15   n-C.sub.6 H.sub.13                                                        16   n-C.sub.7 H.sub.15                                                        17   n-C.sub.8 H.sub.17                                                        18   n-C.sub.9 H.sub.19                                                        19   n-C.sub.10 H.sub.21                                                       20   cyclopropyl                                                               21   1-methyl-cycloprop-1-yl                                                   22   cyclobutyl                                                                23   cyclopentyl                                                               24   cyclohexyl                                                                25   cyclohex-1-en-1-yl                                                        26   methoxymethyl                                                             27   ethoxymethyl                                                              28   phenoxymethyl                                                             29   benzyloxymethyl                                                           30   phenylmethyl                                                              31   morpholino-N-methyl                                                       32   phenylthiomethyl                                                          33   2-methylphenyl                                                            34   3-methylphenyl                                                            35   4-methylphenyl                                                            36   2-chlorophenyl                                                            37   3-chlorophenyl                                                            38   4-chlorophenyl                                                            39   2-bromophenyl                                                             40   3-bromophenyl                                                             41   4-bromophenyl                                                             42   2-fluorophenyl                                                            43   3-fluorophenyl                                                            44   4-fluorophenyl                                                            45   2-iodophenyl                                                              46   3-iodophenyl                                                              47   4-iodophenyl                                                              48   2-methoxyphenyl                                                           49   3-methoxyphenyl                                                           50   4-methoxyphenyl                                                           51   2-ethoxyphenyl                                                            52   3-ethoxyphenyl                                                            53   4-ethoxyphenyl                                                            54   2-n-propoxyphenyl                                                         55   3-n-propoxyphenyl                                                         56   4-n-propoxyphenyl                                                         57   2-i-propoxyphenyl                                                         58   3-i-propoxyphenyl                                                         59   4-i-propoxyphenyl                                                         60   2-n-butoxyphenyl                                                          61   3-n-butoxyphenyl                                                          62   4-n-butoxyphenyl                                                          63   2-sec.-butoxyphenyl                                                       64   3-sec.-butoxyphenyl                                                       65   4-sec.-butoxyphenyl                                                       66   2-iso-butoxyphenyl                                                        67   3-isobutoxyphenyl                                                         68   4-isobutoxyphenyl                                                         69   2-tert.-butoxyphenyl                                                      70   3-tert.-butoxyphenyl                                                      71   4-tert.-butoxyphenyl                                                      72   2-ethylphenyl                                                             73   3-ethylphenyl                                                             74   4-ethylphenyl                                                             75   2-n-propylphenyl                                                          76   3-n-propylphenyl                                                          77   4-n-propylphenyl                                                          78   2-i-propylphenyl                                                          79   3-i-propylphenyl                                                          80   4-i-propylphenyl                                                          81   2-n-butylphenyl                                                           82   3-n-butylphenyl                                                           83   4-n-butylphenyl                                                           84   2-isobutylphenyl                                                          85   3-isobutylphenyl                                                          86   4-isobutylphenyl                                                          87   2-sec.-butylphenyl                                                        88   3-sec.-butylphenyl                                                        89   4-sec.-butylphenyl                                                        90   2-tert.-butylphenyl                                                       91   3-tert.-butylphenyl                                                       92   4-tert.-butylphenyl                                                       93   2-NO.sub.2 -phenyl                                                        94   3-NO.sub.2 -phenyl                                                        95   4-NO.sub.2 -phenyl                                                        96   2-CF.sub.3 -phenyl                                                        97   3-CF.sub.3 -phenyl                                                        98   4-CF.sub.3 -phenyl                                                        99   2-CN-phenyl                                                               100  3-CN-phenyl                                                               101  4-CN-phenyl                                                               102  2-(CH.sub.2 CN)-phenyl                                                    103  3-(CH.sub.2 CN)-phenyl                                                    104  4-(CH.sub.2 CN)-phenyl                                                    105  2-CH.sub.3 CO-phenyl                                                      106  3-CH.sub.3 CO-phenyl                                                      107  4-CH.sub.3 CO-phenyl                                                      108  2-CHO-phenyl                                                              109  3-CHO-phenyl                                                              110  4-CHO-phenyl                                                              111  2-NMe.sub.2 -phenyl                                                       112  3-NMe.sub.2 -phenyl                                                       113  4-NMe.sub.2 -phenyl                                                       114  2-CO.sub.2 Me-phenyl                                                      115  3-CO.sub.2 Me-phenyl                                                      116  4-CO.sub.2 Me-phenyl                                                      117  2-CO.sub.2 Et-phenyl                                                      118  3-CO.sub.2 Et-phenyl                                                      119  4-CO.sub.2 Et-phenyl                                                      120  2-OCF.sub.3 -phenyl                                                       121  3-OCF.sub.3 -phenyl                                                       122  4-OCF.sub.3 -phenyl                                                       123  2-phenyl-phenyl                                                           124  3-phenyl-phenyl                                                           125  4-phenyl-phenyl                                                           126  2-phenoxy-phenyl                                                          127  3-phenoxy-phenyl                                                          128  4-phenoxy-phenyl                                                          129  3,4-OCH.sub.2 O-phenyl                                                    130  3,4-OCH.sub.2 CH.sub.2 -phenyl                                            131  3,4,5-(OCH.sub.3).sub.3 -phenyl                                           132  3,4-(OCH.sub.3).sub.2 -phenyl                                             133  2,3-Me.sub.2 -phenyl                                                      134  2,4-Me.sub.2 -phenyl                                                      135  2,5-Me.sub.2 -phenyl                                                      136  2,6-Me.sub.2 -phenyl                                                      137  3,4-Me.sub.2 -phenyl                                                      138  3,5-Me.sub.2 -phenyl                                                      139  2,4,6-Me.sub.3 -phenyl                                                    140  2,3-Cl.sub.2 -phenyl                                                      141  2,4-Cl.sub.2 -phenyl                                                      142  2,5-Cl.sub.2 -phenyl                                                      143  2,6-Cl.sub.2 -phenyl                                                      144  3,4-Cl.sub.2 -phenyl                                                      145  3,5-Cl.sub.2 -phenyl                                                      146  2-methyl, 5-NO.sub.2 -phenyl                                              147  2-methyl, 3-NO.sub.2 -phenyl                                              148  2-methyl, 4-F-phenyl                                                      149  4-methyl, 3-F-phenyl                                                      150  2,6-Cl.sub.2, 4-NO.sub.2 -phenyl                                          151  2-NO.sub.2, 4-Cl-phenyl                                                   152  2-Cl, 5-CF.sub.3 -phenyl                                                  153  4-Cl, 3-CF.sub.3 -phenyl                                                  154  2-methyl, 4-CH.sub.3 CO-phenyl                                            155  2-methyl, 5-CH.sub.3 CO-phenyl                                            156  2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl                                        157  2-Me, 4-methoximinomethyl-phenyl                                          158  2-Me, 5-methoximinomethyl-phenyl                                          159  2,5-Me.sub.2, 4-methoximinomethyl-phenyl                                  160  2-Me, 4-ethoximinomethyl-phenyl                                           161  2-Me, 4-n-propoximinomethyl-phenyl                                        162  2-Me, 4-i-propoximinomethyl-phenyl                                        163  2-Me, 4-n-butoximinomethyl-phenyl                                         164  2-Me, 5-ethoximinomethyl-phenyl                                           165  2,5-Me.sub.2, 4-ethoximinomethylphenyl                                    166  3-(5-phenyl-1,3,4-oxadiazol-2-yl)-phenyl                                  167  3-(5-naphthyl-1,3,4-oxadiazol-2-yl)-phenyl                                168  2-pyridyl                                                                 169  3-pyridyl                                                                 170  4-pyridyl                                                                 171  5-methyl-2-pyridyl                                                        172  6-methyl-2-pyridyl                                                        173  quinolin-3-yl                                                             174  2,8(CF.sub.3).sub.2 -quinolin-4-yl                                        175  Isoquinolin-4-yl                                                          176  thien-2-yl                                                                177  thien-3-yl                                                                178  2-chloro-thien-3-yl                                                       179  2-chloro-thien-4-yl                                                       180  3-chloro-thien-2-yl                                                       181  2-chloro-thien-5-yl                                                       182  2,5-Cl.sub.2 -thien-3-yl                                                  183  3-furyl                                                                   184  2-(isoxazol-3-yl)-thien-5-yl                                              185  2-cyano-thien-3-yl                                                        186  3-Me-thien-2-yl                                                           187  2-NO.sub.2 -thien-5-yl                                                    188  3-benzothienyl                                                            189  3,5-Me.sub.2 -isoxazol-3-yl                                               190  2-thiazolyl                                                               191  5-NO.sub.2 -thiazol-2-yl                                                  192  5-NO.sub.2 -imidazol-4-yl                                                 193  4-pyrrazolyl                                                              194  3,5-Me.sub.2 -pyrrazol-4-yl                                               195  3-(4-Cl-phenyl)-isoxazol-5-yl                                                                         107-110° C.                                 196  4-chloro-3-(3-chlorophenyl)-isoxazol-5-yl                                 197  5-(4-methylphenyl)-1,3,4-oxadiazol-2-yl                                   198  5-phenyl-1,3,4-thiadiazol-2-yl                                            199  3-(4-chlorophenyl-1,2,4-oxadiazol-5-yl                                    200  3-isopropyl-isoxazol-5-yl                                                 201  5-(4-F-phenyl)-isoxazol-3-yl                                              202  4-ethyl-5-phenyl-isoxazol-3-yl                                            203  4-chloro-5-(3-Cl-phenyl)-isoxazol-3-yl                                    204  CH.sub.2 Br                                                               205  CH.sub.2 Cl                                                               206  CH.sub.2 I                                                                207  1-naphthyl                                                                208  2-naphthyl                                                                209  6-methoxy-napht-2-yl                                                      ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                          ##STR18##                                                                                                 phys. data                                                                     (m.p.  °C.!);                                                           IR  cm.sup.-1 !;                                   No.  R                      .sup.1 H-NMR  δ scale!                       ______________________________________                                         1    H                      3.17(CH); 3.87;                                                                4.07(Me);                                                                      7.27-7.60(aryl)                                    2    SiMe.sub.3             0.22; 3.86;                                                                    4.06(Me);                                                                      7.25-7.61(aryl)                                    3    SnMe.sub.3                                                                4    I                                                                         5    CN                                                                        6    CH.sub.3                                                                  7    CH.sub.2 CH.sub.3                                                         8    n-C.sub.3 H.sub.7                                                         9    i-C.sub.3 H.sub.7                                                         10   n-C.sub.4 H.sub.9                                                         11   i-C.sub.4 H.sub.9                                                         12   s-C.sub.4 H.sub.9                                                         13   t-C.sub.4 H.sub.9                                                         14   n-C.sub.5 H.sub.11                                                        15   n-C.sub.6 H.sub.13                                                        16   n-C.sub.7 H.sub.15                                                        17   n-C.sub.8 H.sub.17                                                        18   n-C.sub.9 H.sub.19                                                        19   n-C.sub.10 H.sub.21                                                       20   cyclopropyl                                                               21   1-methyl-cycloprop-1-yl                                                   22   cyclobutyl                                                                23   cyclopentyl                                                               24   cyclohexyl             1.23-2.61                                                                      (cyclohexyl);                                                                  3.85; 4.05(Me);                                                                7.22-7.48(aryl)                                    25   cyclohex-1-en-1-yl     98-100° C.                                  26   methoxymethyl          3.41; 3.87;                                                                    4.07(Me);                                                                      4.28(CH.sub.2);                                                                7.28-7.55(aryl)                                    27   ethoxymethyl                                                              28   phenoxymethyl                                                             29   benzyloxymethyl                                                           30   phenylmethyl                                                              31   morpholino-N-methyl    2.59; 3.49;                                                                    3.76(CH.sub.2);                                                                3.87; 4.07(Me);                                                                7.23-7.71(aryl)                                    32   phenylthiomethyl                                                          33   3-methyl-phenyl        95-99° C.                                   34   3-chloro-phenyl        3.86; 4.09(Me);                                                                7.25-7.63(aryl)                                    35   4-chloro-phenyl        91-96° C.                                   36   3-bromo-phenyl                                                            37   3-fluorophenyl                                                            38   4-fluorophenyl                                                            39   2-iodo-phenyl                                                             40   3-iodo-phenyl                                                             41   4-iodo-phenyl                                                             42   3-methoxy-phenyl       3.82; 3.84;                                                                    4.08(Me);                                                                      6.87-7.63(aryl)                                    43   4-methoxy-phenyl       118-121° C.                                 44   2-ethoxy-phenyl                                                           45   3-ethoxy-phenyl                                                           46   4-ethoxy-phenyl        1.42; 3.84;                                                                    4.07(Me);                                                                      4.05(CH.sub.2);                                                                6.84-7.61(aryl)                                    47   2-n-propoxy-phenyl                                                        48   3-n-propoxy-phenyl                                                        49   4-n-propoxy-phenyl                                                        50   2-i-propoxy-phenyl                                                        51   3-i-propoxy-phenyl     1.34; 3.87;                                                                    4.08(Me);                                                                      4.57(CH);                                                                      6.75-7.61(aryl)                                    52   4-i-propoxy-phenyl                                                        53   2-n-butoxy-phenyl                                                         54   3-n-butoxy-phenyl                                                         55   5-n-butoxy-phenyl                                                         56   2-sec.-butoxy-phenyl                                                      57   3-sec.-butoxy-phenyl                                                      58   4-sec.-butoxy-phenyl                                                      59   2-iso-butoxy-phenyl                                                       60   3-iso-butoxy-phenyl                                                       61   4-iso-butoxy-phenyl                                                       62   2-tert.-butoxyphenyl                                                      63   3-tert.-butoxyphenyl                                                      64   4-tert.-butoxyphenyl                                                      65   2-ethyl-phenyl                                                            66   3-ethyl-phenyl                                                            67   4-ethyl-phenyl         1.23; 3.84;                                                                    4.09(Me);                                                                      2.65(CH.sub.2);                                                                7.17-7.63(aryl)                                    68   2-n-propyl-phenyl                                                         69   3-n-propyl-phenyl                                                         70   4-n-propyl-phenyl                                                         71   2-i-propyl-phenyl                                                         72   3-i-propyl-phenyl                                                         73   4-i-propyl-phenyl      1.24; 3.85;                                                                    4.09(Me);                                                                      2.91(CH);                                                                      7.20-7.61(aryl)                                    74   2-n-butylphenyl                                                           75   3-n-butylphenyl                                                           76   4-n-butylphenyl                                                           77   2-iso-butyl-phenyl                                                        78   3-iso-butyl-phenyl                                                        79   4-iso-butyl-phenyl                                                        80   2-sec.-butylphenyl                                                        81   3-sec.-butylphenyl                                                        82   4-sec.-butylphenyl                                                        83   2-tert.-butylphenyl                                                       84   3-tert.-butylphenyl                                                       85   4-tert.-butylphenyl    1.31; 3.85;                                                                    4.09(Me);                                                                      7.35-7.61(aryl)                                    86   3-NO.sub.2 -phenyl     122-125° C.                                 87   4-NO.sub.2 -phenyl     160-164° C.                                 88   2-CF.sub.3 -phenyl     66-70° C.                                   89   3-CF.sub.3 -phenyl     3.86; 4.09(Me);                                                                7.33-7.73(aryl)                                    90   2-CN-phenyl                                                               91   3-CN-phenyl                                                               92   4-CN-phenyl            145-149° C.                                 93   2-(CH.sub.2 CN)-phenyl 3.82; 4.04(Me);                                                                3.92(CH.sub.2);                                                                7.25-7.65(aryl)                                    94   3-(CH.sub.2 CN)-phenyl 3.75(CH.sub.2);                                                                3.84; 4.08(Me);                                                                7.33-7.63(aryl)                                    95   4-(CH.sub.2 CN)-phenyl 85-90° C.                                   96   2-CH.sub.3 CO-phenyl                                                      97   3-CH.sub.3 CO-phenyl                                                      98   4-CH.sub.3 CO-phenyl   121-123° C.                                 99   2-CHO-phenyl                                                              100  3-CHO-phenyl           3.87; 4.10(Me);                                                                7.36-7.94(aryl);                                                               10.01(CH)                                          101  4-CHO-phenyl           104-106° C.                                 102  2-NMe.sub.2 -phenyl                                                       103  3-NMe.sub.2 -phenyl                                                       104  4-NMe.sub.2 -phenyl    2.99; 3.82;                                                                    4.06(Me);                                                                      6.59-7.55(aryl)                                    105  2-CO.sub.2 Me-phenyl                                                      106  3-CO.sub.2 Me-phenyl   3.86; 3.94;                                                                    4.09(Me);                                                                      7.35-8.14(aryl)                                    107  4-CO.sub.2 Me-phenyl                                                      108  2-CO.sub.2 Et-phenyl                                                      109  3-CO.sub.2 Et-phenyl                                                      110  4-CO.sub.2 Et-phenyl                                                      111  2-OCF.sub.3 -phenyl                                                       112  3-OCF.sub.3 -phenyl                                                       113  4-OCF.sub.3 -phenyl                                                       114  2-phenyl-phenyl        3.79; 4.01(Me);                                                                7.23-7.61(aryl)                                    115  3-phenyl-phenyl        3.85; 4.09(Me);                                                                7.38-7.73(aryl)                                    116  4-phenyl-phenyl        137-142° C.                                 117  2-phenoxy-phenyl                                                          118  3-phenoxy-phenyl                                                          119  4-phenoxy-phenyl       3.82; 4.07(Me);                                                                6.92-7.58(aryl)                                    120  3,4-OCH.sub.2 O-phenyl 3.84; 4.07(Me);                                                                5.98(CH.sub.2);                                                                6.76-7.58(aryl)                                    121  3,4-OCH.sub.2 CH.sub.2 O-phenyl                                                                       3.84; 4.07(Me);                                                                4.25(CH.sub.2);                                                                6.79-7.58(aryl)                                    122  3,4,5-(OCH.sub.3).sub.3 -phenyl                                                                       3.86; 3.88;                                                                    3.89; 3.92;                                                                    4.10(Me);                                                                      6.75-7.61(aryl)                                    123  3,4-(OCH.sub.3).sub.2 -phenyl                                             124  2,3-Me.sub.2 -phenyl   105-109° C.                                 125  2,4-Me.sub.2 -phenyl   104-109° C.                                 126  2,5-Me.sub.2 -phenyl   142-147° C.                                 127  2,6-Me.sub.2 -phenyl                                                      128  3,4-Me.sub.2 -phenyl   86-89° C.                                   129  3,5-Me.sub.2 -phenyl   2.30(2x); 3.84;                                                                4.08(Me);                                                                      6.97-7.61(aryl)                                    130  2,4,6-Me.sub.3 -phenyl 108-112° C.                                 131  2,3-Cl.sub.2 -phenyl   117-121° C.                                 132  2,4-Cl.sub.2 -phenyl   113-116° C.                                 133  2,5-Cl.sub.2 -phenyl   107-110° C.                                 134  2,6-Cl.sub.2 -phenyl   145-148° C.                                 135  3,4-Cl.sub.2 -phenyl   93-96° C.                                   136  3,5-Cl.sub.2 -phenyl   106-109° C.                                 137  2-methyl, 5-NO.sub.2 -phenyl                                              138  2-methyl, 3-NO.sub.2 -phenyl                                              139  2-methyl, 4-F-phenyl                                                      140  4-methyl, 3-F-phenyl                                                      141  2,6-Cl.sub.2, 4-NO.sub.2 -phenyl                                          142  2-NO.sub.2, 4-Cl-phenyl                                                   143  2-Cl, 5-CF.sub.3 -phenyl                                                                              3.87; 4.07(Me);                                                                7.35-8.37(aryl)                                    144  4-Cl, 3-CF.sub.3 -phenyl                                                  145  2-methyl, 4-CH.sub.3 CO-phenyl                                            146  2-methyl, 5-CH.sub.3 CO-phenyl                                            147  2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl                                        148  2-Me, 4-methoximinomethyl-phenyl                                                                      2.22; 2.46;                                                                    3.86; 4.01;                                                                    4.09(Me);                                                                      7.20-7.75(aryl)                                    149  2-Me, 5-methoximinomethyl-phenyl                                                                      2.22; 2.45;                                                                    3.84; 3.99;                                                                    4.06(Me);                                                                      7.17-7.71(aryl)                                    150  2,5-Me.sub.2, 4-methoximinomethyl-phenyl                                  151  2-Me, 4-ethoximinomethyl-phenyl                                           152  2-Me, 4-n-propoximinomethyl-phenyl                                        153  2-Me, 4-i-propoximinomethyl-phenyl                                        154  2-Me, 4-n-butoximinomethyl-phenyl                                         155  2-Me, 5-ethoximinomethyl-phenyl                                           156  2,5-Me.sub.2, 4-ethoximinomethyl-phenyl                                   157  1-Me-2-naphthyl                                                           158  1-naphthyl             3.82; 4.09(Me);                                                                7.35-8.37(aryl)                                    159  2-naphthyl             114-118° C.                                 160  6-methoxy-2-naphthyl   3.86; 3.95;                                                                    4.11(Me);                                                                      7.12-7.94(aryl)                                    161                                                                                  ##STR19##             2240 (CC, RAMAN)                                   162                                                                                  ##STR20##             1725; 1441; 1258; 1209; 1069; 1037; 1013;                                      950                                                      ##STR21##                                                                163                                                                                  ##STR22##             1727; 1437; 1324; 1309; 1264; 1215; 1069;                                      1040                                                     ##STR23##                                                                164  3-(5-phenyl-1,3,4-oxadiazol-2-yl)-phenyl                                                              44-52° C.                                   165  3-(5-naphthyl-1,3,4-oxadiazol-2-yl)-phenyl                                166  2-pyridyl              3.87; 4.09(Me);                                                                7.22-8.62(8H)                                      167  3-pyridyl              78-82° C.                                   168  4-pyridyl                                                                 169  5-methyl-2-pyridyl                                                        170  6-methyl-2-pyridyl                                                        171  quinolin-3-yl                                                             172  2,8(CF.sub.3).sub.2 -quinolin-4-yl                                        173  isoquinolin-4-yl                                                          174  thien-2-yl             3.87; 4.09(Me);                                                                6.95-7.58(aryl)                                    175  thien-3-yl             80-89° C.                                   176  2-chloro-thien-3-yl                                                       177  2-chloro-thien-4-yl    3.84; 4.07(Me);                                                                6.98-7.58(aryl)                                    178  3-chloro-thien-2-yl    3.88; 4.09(Me);                                                                6.93-7.66(aryl)                                    179  2-chloro-thien-5-yl    3.87; 4.08(Me);                                                                6.81-7.59(aryl)                                    180  2,5-Cl.sub.2 -thien-3-yl                                                  181  3-furyl                                                                   182  2-(isoxazol-3-yl)-thien-5-yl                                              183  2-cyano-thien-3-yl                                                        184  3-Me-thien-2-yl                                                           185  2-NO.sub.2 -thien-5-yl                                                    186  3-benzothienyl                                                            187  3,5-Me.sub.2 -isoxazol-3-yl                                               188  2-thiazolyl                                                               189  5-NO.sub.2 -thiazol-2-yl                                                  190  5-NO.sub.2 -imidazol-4-yl                                                 191  4-pyrrazolyl                                                              192  3,5-Me.sub.2 -pyrrazol-4-yl                                               193  3-(4-Cl-phenyl)-isoxazol-5-yl                                             194  4-chloro-3-(3-chlorophenyl)-isoxazol-5-yl                                 195  5-(4-methylphenyl)-1,3,4-oxadiazol-2-yl                                   196  5-phenyl-1,3,4-thiadiazol-2-yl                                            197  3-(4-chlorophenyl)-1,2,4-oxadiazol-5-yl                                   198  3-isopropyl-isoxazol-5-yl                                                 199  5-(4-F-phenyl)-isoxazol-3-yl                                              200  4-ethyl-5-phenyl-isoxazol-3-yl                                            201  4-chloro-5-(3-Cl-phenyl)-isooxalzol-3-yl                                  202  CH.sub.2 Br                                                               203  CH.sub.2 Cl                                                               204  CH.sub.2 I                                                                205  9-anthracenyl          159-164° C.                                 206  2-methoxy-naphth-1-yl  129-137° C.                                 207  CHCH-phenyl            97-102° C.                                  208  4-(benzthiazol-2-yl)-phenyl                                                                           164-168° C.                                 209  1-pyrenyl              179-183° C.                                 ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                          ##STR24##                                                                                                 phys. data (m.p.                                                                °C.!);                                                                 IR  cm.sup.-1 !;                                   No.   R                     .sup.1 H-NMR  δ scale!                       ______________________________________                                         1     H                                                                        2     SiMe.sub.3                                                               3     SnMe.sub.3                                                               4     I                                                                        5     CN                                                                       6     CH.sub.3                                                                 7     CH.sub.2 CH.sub.3                                                        8     n-C.sub.3 H.sub.7                                                        9     i-C.sub.3 H.sub.7                                                        10    n-C.sub.4 H.sub.9                                                        11    i-C.sub.4 H.sub.9                                                        12    s-C.sub.4 H.sub.9                                                        13    t-C.sub.4 H.sub.9                                                        14    n-C.sub.5 H.sub.11                                                       15    n-C.sub.6 H.sub.13                                                       16    n-C.sub.7 H.sub.15                                                       17    n-C.sub.8 H.sub.17                                                       18    n-C.sub.9 H.sub.19                                                       19    n-C.sub.10 H.sub.21                                                      20    cyclopropyl                                                              21    1-methyl-cycloprop-1-yl                                                  22    cyclobutyl                                                               23    cyclopentyl                                                              24    cyclohexyl                                                               25    cyclohex-1-en-1-yl                                                       26    methoxymethyl                                                            27    ethoxymethyl                                                             28    phenoxymethyl                                                            29    benzyloxymethyl                                                          30    phenylmethyl                                                             31    morpholino-N-methyl                                                      32    phenylthiomethyl                                                         33    3-methyl-phenyl                                                          34    3-chloro-phenyl                                                          35    4-chloro-phenyl                                                          36    3-bromo-phenyl                                                           37    3-fluorophenyl                                                           38    4-fluorophenyl                                                           39    2-iodo-phenyl                                                            40    3-iodo-phenyl                                                            41    4-iodo-phenyl                                                            42    3-methoxy-phenyl                                                         43    4-methoxy-phenyl                                                         44    2-ethoxy-phenyl                                                          45    3-ethoxy-phenyl                                                          46    4-ethoxy-phenyl                                                          47    2-n-propoxy-phenyl                                                       48    3-n-propoxy-phenyl                                                       49    4-n-propoxy-phenyl                                                       50    2-i-propoxy-phenyl                                                       51    3-i-propoxy-phenyl                                                       52    4-i-propoxy-phenyl                                                       53    2-n-butoxy-phenyl                                                        54    3-n-butoxy-phenyl                                                        55    4-n-butoxy-phenyl                                                        56    2-sec.-butoxy-phenyl                                                     57    3-sec.-butoxy-phenyl                                                     58    4-sec.-butoxy-phenyl                                                     59    2-iso-butoxy-phenyl                                                      60    3-iso-butoxy-phenyl                                                      61    4-iso-butoxy-phenyl                                                      62    2-tert.-butoxyphenyl                                                     63    3-tert.-butoxyphenyl                                                     64    4-tert.-butoxyphenyl                                                     65    2-ethyl-phenyl                                                           66    3-ethyl-phenyl                                                           67    4-ethyl-phenyl                                                           68    2-n-propyl-phenyl                                                        69    3-n-propyl-phenyl                                                        70    4-n-propyl-phenyl                                                        71    2-i-propyl-phenyl                                                        72    3-i-propyl-phenyl                                                        73    4-i-propyl-phenyl                                                        74    2-n-butylphenyl                                                          75    3-n-butylphenyl                                                          76    4-n-butylphenyl                                                          77    2-iso-butyl-phenyl                                                       78    3-iso-butyl-phenyl                                                       79    4-iso-butyl-phenyl                                                       80    2-sec.-butylphenyl                                                       81    3-sec.-butylphenyl                                                       82    4-sec.-butylphenyl                                                       83    2-tert.-butylphenyl                                                      84    3-tert.-butylphenyl                                                      85    4-tert.-butylphenyl                                                      86    3-NO.sub.2 -phenyl                                                       87    4-NO.sub.2 -phenyl                                                       88    2-CF.sub.3 -phenyl                                                       89    3-CF.sub.3 -phenyl                                                       90    2-CN-phenyl                                                              91    3-CN-phenyl                                                              92    4-CN-phenyl                                                              93    2-(CH.sub.2 CN)-phenyl                                                   94    3-(CH.sub.3 CN)-phenyl                                                   95    4-(CH.sub.2 CN)-phenyl)                                                  96    2-CH.sub.3 CO-phenyl                                                     97    3-CH.sub.3 CO-phenyl                                                     98    4-CH.sub.3 CO-phenyl                                                     99    2-CHO-phenyl                                                             100   3-CHO-phenyl                                                             101   4-CHO-phenyl                                                             102   2-NMe.sub.2 -phenyl                                                      103   3-NMe.sub.2 -phenyl                                                      104   4-NMe.sub.2 -phenyl                                                      105   2-CO.sub.2 Me-phenyl                                                     106   3-CO.sub.2 Me-phenyl                                                     107   4-CO.sub.2 Me-phenyl                                                     108   2-CO.sub.2 Et-phenyl                                                     109   3-CO.sub.2 Et-phenyl                                                     110   4-CO.sub.2 Et-phenyl                                                     111   2-OCF.sub.3 -phenyl                                                      112   3-OCF.sub.3 -phenyl                                                      113   4-OCF.sub.3 -phenyl                                                      114   2-phenyl-phenyl                                                          115   3-phenyl-phenyl                                                          116   4-phenyl-phenyl                                                          117   2-phenoxy-phenyl                                                         118   3-phenoxy-phenyl                                                         119   4-phenoxy-phenyl                                                         120   3,4-OCH.sub.2 O-phenyl                                                   121   3,4-OCH.sub.2 CH.sub.2 -phenyl                                           122   3,4,5-(OCH.sub.3).sub.3 -phenyl                                          123   3,4-(OCH.sub.3).sub.2 -phenyl                                            124   2,3-Me.sub.2 -phenyl                                                     125   2,4-Me.sub.2 -phenyl                                                     126   2,5-Me.sub.2 -phenyl                                                     127   2,6-Me.sub.2 -phenyl                                                     128   3,4-Me.sub.2 -phenyl                                                     129   3,5-Me.sub.2 -phenyl                                                     130   2,4,6-Me.sub.3 -phenyl                                                   131   2,3-Cl.sub.2 -phenyl                                                     132   2,4-Cl.sub.2 -phenyl                                                     133   2,5-Cl.sub.2 -phenyl                                                     134   2,6-Cl.sub.2 -phenyl                                                     135   3,4-Cl.sub.2 -phenyl                                                     136   3,5-Cl.sub.2 -phenyl                                                     137   2-methly, 5-NO.sub.2 -phenyl                                             138   2-methyl, 3-NO.sub.2 -phenyl                                             139   2-methyl, 4-F-phenyl                                                     140   4-methyl, 3-F-phenyl                                                     141   2,6-Cl.sub.2, 4-NO.sub.2 -phenyl                                         142   2-NO.sub.2, 4-Cl-phenyl                                                  143   2-Cl, 5-CF.sub.3 -phenyl                                                 144   4-Cl, 3-CF.sub.3 -phenyl                                                 145   2-methyl, 4-CH.sub.3 CO-phenyl                                           146   2-methyl, 5-CH.sub.3 CO-phenyl                                           147   2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl                                       148   2-Me, 4-methoximinomethyl-phenyl                                         149   2-Me, 5-methoximinomethyl-phenyl                                         150   2,5-Me.sub.2, 4-methoximinomethyl-phenyl                                 151   2-Me, 4-ethoximinomethyl-phenyl                                          152   2-Me, 4-n-propoximinomethyl-phenyl                                       153   2-Me, 4-i-propoximinomethyl-phenyl                                       154   2-Me, 4-n-butoximinomethyl-phenyl                                        155   2-Me, 5-ethoximinomethyl-phenyl                                          156   2,5-Me.sub.2, 4-ethoximinomethyl-phenyl                                  157   1-Me-2-naphthyl                                                          158   1-naphthyl                                                               159   2-naphthyl                                                               160   6-methoxy-2-naphthyl                                                     161   3-(5-phenyl-1,3,4-oxadiazol-2-yl)-                                             phenyl                                                                   162   3-(5-naphthyl-1,3,4,-oxa-                                                      diazol-2-yl)-phenyl                                                      163   2-pyridyl                                                                164   3-pyridyl                                                                165   4-pyridyl                                                                166   5-methyl-2-pyridyl                                                       167   6-methyl-pyridyl                                                         168   quinolin-3-yl                                                            169   2,8(CF.sub.3).sub.2 -quinolin-4-yl                                       170   isoquinolin-4-yl                                                         171   thien-2-yl                                                               172   thien-3-yl                                                               173   2-chloro-thien-3-yl                                                      174   2-chloro-thien-4-yl                                                      175   3-chloro-thien-2-yl                                                      176   2-chloro-thien-5-yl                                                      177   2,5-Cl.sub.2 -thien-3-yl                                                 178   3-furyl                                                                  179   2-(isoxazol-3-yl)-thien-5-yl                                             180   2-cyano-thien-3-yl                                                       181   3-Me-thien-2-yl                                                          182   2-NO.sub.2 -thien-5-yl                                                   183   3-benzothienyl                                                           184   3,5-Me.sub.2 -isoxazol-3-yl                                              185   2-thiazolyl                                                              186   5-NO.sub.2 -thiazol-2-yl                                                 187   5-NO.sub.2 -imidazol-4-yl                                                188   4-pyrrazolyl                                                             189   3,5-Me.sub.2 -pyrrazol-4-yl                                              190   5-NO.sub.2 -imidazol-4-yl                                                191   3-(4-Cl-phenyl)-isoxazol-5-yl                                            192   4-chloro-3-(3-chlorophenyl)-                                                   isoxazol-5-yl                                                            193   5-(4-methylphenyl)-1,3,4-                                                      oxadiazol-2-yl                                                           194   5-phenyl-1,3,4-thiadiazol-2-yl                                           195   3-(4-chlorophenyl)-1,2,4-                                                      oxadizaol-5-yl                                                           196   3-isopropyl-isoxazol-5-yl                                                197   5-(4-F-phenyl)-isoxazol-3-yl                                             198   4-ethyl-5-phenyl-isoxazol-3-yl                                           199   4-chloro-5-(3-Cl-phenyl)-                                                      isooxazol-3-yl                                                           200   CH.sub.2 Br                                                              201   CH.sub.2 Cl                                                              202   CH.sub.2 I                                                               ______________________________________                                    

                  TABLE 4                                                          ______________________________________                                          ##STR25##                                                                                                phys. data (m.p.                                                                °C.!;                                                                  IR  cm.sup.-1 !;                                    No.   R                    .sup.1 H-NMR  δ scale!                        ______________________________________                                         1     H                    2.99; 3.98(Me);                                                                3.13(H); 6.80                                                                  (NH); 7.21-7.58                                                                (aryl)                                              2     SiMe.sub.3                                                               3     SnMe.sub.3                                                               4     I                                                                        5     CN                                                                       6     CH.sub.2 CH.sub.3                                                        7     n-C.sub.3 H.sub.7                                                        8     i-C.sub.3 H.sub.7                                                        9     n-C.sub.4 H.sub.9                                                        10    i-C.sub.4 H.sub.9                                                        11    s-C.sub.4 H.sub.9                                                        12    t-C.sub.4 H.sub.9                                                        13    n-C.sub.5 H.sub.11                                                       14    n-C.sub.6 H.sub.13                                                       15    n-C.sub.7 H.sub.15                                                       16    n-C.sub.8 H.sub.17                                                       17    n-C.sub.9 H.sub.19                                                       18    n-C.sub.10 H.sub.21                                                      19    cyclopropyl                                                              20    1-methyl-cycloprop-1-yl                                                  21    cyclobutyl                                                               22    cyclopentyl                                                              23    cyclohexyl                                                               24    cyclohex-1-en-1-yl                                                       25    methoxymethyl                                                            26    ethoxymethyl                                                             27    phenoxymethyl                                                            28    benzyloxymethyl                                                          29    phenylmethyl                                                             30    morpholino-N-methyl                                                      31    phenylthiomethyl                                                         32    2-methyl-phenyl      128-129° C.                                  33    3-methly-phenyl                                                          34    4-methyl-phenyl                                                          35    2-chloro-phenyl                                                          36    3-chloro-phenyl                                                          37    4-chloro-phenyl                                                          38    2-bromo-phenyl                                                           39    3-bromo-phenyl                                                           40    3-bromo-phenyl                                                           41    2-flurophenyl                                                            42    3-fluorophenyl                                                           43    4-fluorophenyl                                                           44    2-iodo-phenyl                                                            45    3-iodo-phenyl                                                            46    4-iodo-phenyl                                                            47    2-methoxy-phenyl                                                         48    3-methoxy-phenyl                                                         49    4-methoxy-phenyl                                                         50    2-ethoxy-phenyl                                                          51    3-ethoxy-phenyl                                                          52    4-ethoxy-phenyl                                                          53    2-n-propoxy-phenyl                                                       54    3-n-propoxy-phenyl                                                       55    4-n-propoxy-phenyl                                                       56    2-i-propoxy-phenyl                                                       57    3-i-propoxy-phenyl                                                       58    4-i-propoxy-phenyl                                                       59    2-n-butoxy-phenyl                                                        60    3-n-butoxy-phenyl                                                        61    4-n-butoxy-phenyl                                                        62    2-sec.-butoxy-phenyl                                                     63    3-sec.-butoxy-phenyl                                                     64    4-sec.-butoxy-phenyl                                                     65    2-iso-butoxy-phenyl                                                      66    3-iso-butoxy-phenyl                                                      67    4-iso-butoxy-phenyl                                                      68    2-tert.-butoxyphenyl                                                     60    3-tert.-butoxyphenyl                                                     70    4-tert.-butoxyphenyl                                                     71    2-ethyl-phenyl                                                           72    3-ethyl-phenyl                                                           73    4-ethyl-phenyl                                                           74    2-n-propyl-phenyl                                                        75    3-n-propyl-phenyl                                                        76    4-n-propyl-phenyl                                                        77    2-i-propyl-phenyl                                                        78    3-i-propyl-phenyl                                                        79    4-i-propyl-phenyl                                                        80    2-n-butylphenyl                                                          81    3-n-butylphenyl                                                          82    4-n-butylphenyl                                                          83    2-iso-butyl-phenyl                                                       84    3-iso-butyl-phenyl                                                       85    4-iso-butyl-phenyl                                                       86    2-sec.-butylphenyl                                                       87    3-sec.-butylphenyl                                                       88    4-sec.-butylphenyl                                                       89    2-tert.-butylphenyl                                                      90    3-tert.-butylphenyl                                                      91    4-tert.-butylphenyl                                                      92    2-NO.sub.2 -phenyl                                                       93    3-NO.sub.2 -phenyl                                                       94    4-NO.sub.2 -phenyl                                                       95    2-CF.sub.3 -phenyl                                                       96    3-CF.sub.3 -phenyl   139-144° C.                                  97    4-CF.sub.3 -phenyl                                                       98    2-CN-phenyl                                                              99    3-CN-phenyl                                                              100   4-CN-phenyl                                                              101   2-(CH.sub.2 CN)-phenyl                                                                              147-151° C.                                  102   3-(CH.sub.2 CN)-phenyl                                                   103   4-(CH.sub.2 CN)-phenyl                                                   104   2-CH.sub.3 CO-phenyl                                                     105   3-CH.sub.3 CO-phenyl                                                     106   4-CH.sub.3 CO-phenyl                                                     107   2-CHO-phenyl                                                             108   3-CHO-phenyl                                                             109   4-CHO-phenyl                                                             110   2-NMe.sub.2 -phenyl                                                      111   3-NMe.sub.2 -phenyl                                                      112   4-NMe.sub.2 -phenyl                                                      113   2-CO.sub.2 Me-phenyl                                                     114   3-CO.sub.2 Me-phenyl                                                     115   4-CO.sub.2 Me-phenyl                                                     116   2-CO.sub.2 Et-phenyl                                                     117   3-CO.sub.2 Et-phenyl                                                     118   4-CO.sub.2 Et-phenyl                                                     119   2-OCF.sub.3 -phenyl                                                      120   3-OCF.sub.3 -phenyl                                                      121   4-OCF.sub.3 -phenyl                                                      122   2-phenyl-phenyl                                                          123   3-phenyl-phenyl                                                          124   4-phenyl-phenyl                                                          125   2-phenoxy-phenyl                                                         126   3-phenoxy-phenyl                                                         127   4-phenoxy-phenyl                                                         128   3,4-OCH.sub.2 O-phenyl                                                   129   3,4-OCH.sub.2 CH.sub.2 -phenyl                                           130   3,4,5-(OCH.sub.3).sub.3 -phenyl                                          131   3,4-(OCH.sub.3).sub.3 -phenyl                                            132   2,3-Me.sub.2 -phenyl                                                     133   2,4-Me.sub.2 -phenyl                                                     134   2,5-Me.sub.2 -phenyl                                                     135   2,6-Me.sub.2 -phenyl                                                     136   3,4-Me.sub.2 -phenyl                                                     137   3,5-Me.sub.2 -phenyl                                                     138   2,4,6-Me.sub.3 -phenyl                                                   139   2,3-Cl.sub.2 -phenyl 130-132° C.                                  140   2,4-Cl.sub.2 -phenyl 143-145° C.                                  141   2,5-Cl.sub.2 -phenyl 134-137° C.                                  142   2,6-Cl.sub.2 -phenyl                                                     143   3,4-Cl.sub.2 -phenyl 147-150° C.                                  144   3,5-Cl.sub.2 -phenyl 159-163° C.                                  145   2-methyl, 5-NO.sub.2 -phenyl                                             146   2-methyl, 3-NO.sub.2 -phenyl                                             147   2-methyl, 4-F-phenyl                                                     148   4-methyl, 3-F-phenyl                                                     149   2,6-Cl.sub.2, 4-NO.sub.2 -phenyl                                         150   2-NO.sub.2, 4-Cl-phenyl                                                                             192° C.                                      151   2-Cl, 5-CF.sub.3 -phenyl                                                 152   4-Cl, 3-CF.sub.3 -phenyl                                                 153   2-methyl, 4-CH.sub.3 CO-phenyl                                           154   2-methyl, 5-CH.sub.3 CO-phenyl                                           155   2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl                                       156   2-Me, 4-methoximinomethyl-phenyl                                                                    136-140° C.                                  157   2-Me, 5-methoximinomethyl-phenyl                                                                    2,12; 2,45; 2,93;                                                              3,96; 3,99 (Me);                                                               6,79 (NH);                                                                     7,18-7,71 (Aryl)                                    158   2,5-Me.sub.2, 4-methoximinomethyl-phenyl                                 159   2-Me, 4-ethoximinomethyl-phenyl                                          160   2-Me, 4-n-propoximinomethyl-phenyl                                       161   2-Me, 4-i-propoximinomethyl-phenyl                                       162   2-Me, 4-n-butoximinomethyl-phenyl                                        163   2-Me, 5-ethoximinomethyl-phenyl                                          164   2,5-Me.sub.2, 4-ethoximinomethyl-phenyl                                  165   3-(5-phenyl-1,3,4-oxadiazol-2-yl)-                                             phenyl                                                                   166   3-(5-naphthyl-1,3,4-oxa-                                                       diazol-2-yl)-phenyl                                                      167   2-pyridyl                                                                168   3-pyridyl                                                                169   4-pyridyl                                                                170   5-methyl-2-pyridyl                                                       171   6-methyl-2-pyridyl                                                       172   quinolin-3-yl                                                            173   2,8(CF.sub.3).sub.2 -quinolin-4-yl                                       174   isoquinolin-4-yl                                                         175   thien-2-yl                                                               176   thien-3-yl                                                               177   2-chloro-thien-3-yl                                                      178   2-chloro-thien-4-yl                                                      179   3-chloro-thien-2-yl                                                      180   2-chloro-thien-5-yl                                                      181   2,5-Cl.sub.2 -thien-3-yl                                                 182   3-furyl                                                                  183   2-(isoxazol-3-yl)-thien-5-yl                                             184   2-cyano-thien-3-yl                                                       185   3-Me-thien-2-yl                                                          186   2-NO.sub.2 -thien-5-yl                                                   187   3-benzothienyl                                                           188   3,5-Me.sub.2 -isoxazol-3-yl                                              189   2-Thiazolyl                                                              190   5-NO.sub.2 -thiazol-2-yl                                                 191   5-NO.sub.2 -imidazol-4-yl                                                192   4-pyrrazolyl                                                             193   3,5-Me.sub.2 -pyrrazol-4-yl                                              194   3-(4-Cl-phenyl)-isoxazol-5-yl                                            195   4-chloro-3-(3-chlorophenyl)-                                                   isoxazol-5-yl                                                            196   5-(4-methylphenyl)-1,3,4-                                                      oxadiazol-2-yl                                                           197   5-phenyl-1,3,4-thiadiazol-2-yl                                           198   3-(4-chlorophenyl)-1,2,4-                                                      oxadiazol-5-yl                                                           199   3-isopropyl-isoxazol-5-yl                                                200   5-(4-F-phenyl)-isoxazol-3-yl                                             201   4-ethyl-5-phenyl-isoxazol-3-yl                                           202   4-chloro-5-(3-Cl-phenyl)-                                                      isoxazol-3-yl                                                            203   CH.sub.2 Br                                                              204   CH.sub.2 Cl                                                              205   CH.sub.2 I                                                               206   1-naphthyl                                                               207   2-naphthyl           155-158° C.                                  208   6-methoxy-naphth-2-yl                                                    209   CHCH-phenyl          109-112° C.                                  ______________________________________                                    

                  TABLE 5                                                          ______________________________________                                          ##STR26##                                                                                               phys. data                                                                     m. p.  °C.!                                                             IR  cm.sup.-1!                                       No.       R.sup.18        .sup.1 H-NMR  δ scale!                         ______________________________________                                         1         OH                                                                   2         O-methyl                                                             3         O-ethyl                                                              4         O-(n-propyl)                                                         5         O-(i-propyl)                                                         6         O-(n-butyl)                                                          7         O-(i-butyl)                                                          8         O-(s-butyl)                                                          9         O-(tert.-butyl)                                                      10        O-benzyl                                                             11        O-(2-methylbenzyl)                                                   12        O-(3-methylbenzyl)                                                   13        O-(4-methylbenzyl)                                                   14        O-(2-Cl-benzyl)                                                      15        O-(3-Cl-benzyl)                                                      16        O-(4-Cl-benzyl)                                                      17        methyl                                                               18        ethyl                                                                19        n-propyl                                                             20        i-propyl                                                             21        n-butyl                                                              22        i-butyl                                                              23        s-butyl                                                              24        tert.-butyl                                                          25        benzyl                                                               26        phenyl                                                               27        2-Me-phenyl                                                          28        3-Me-phenyl                                                          29        4-Me-phenyl                                                          30        2-F-phenyl                                                           31        3-F-phenyl                                                           32        4-F-phenyl                                                           33        2-Cl-phenyl                                                          34        3-Cl-phenyl                                                          35        4-Cl-phenyl                                                          36        2-Br-phenyl                                                          37        3-Br-phenyl                                                          38        4-Br-phenyl                                                          39        2-I-phenyl                                                           40        3-I-phenyl                                                           41        4-I-phenyl                                                           42        2-CF.sub.3 -phenyl                                                   43        3-CF.sub.3 -phenyl                                                   44        4-CF.sub.3 -phenyl                                                   45        2-OCH.sub.3 -phenyl                                                  46        3-OCH.sub.3 -phenyl                                                  47        4-OCH.sub.3 -phenyl                                                  48        2-CN-phenyl                                                          49        3-CN-phenyl                                                          50        4-CN-phenyl                                                          51        2-NO.sub.2 -phenyl                                                   52        3-NO.sub.2 -phenyl                                                   53        4-NO.sub.2 -phenyl                                                   54        2-OCF.sub.3 -phenyl                                                  55        3-OCF.sub.3 -phenyl                                                  56        4-OCF.sub.3 -phenyl                                                  57        2-CCl.sub.3 -phenyl                                                  58        3-CCl.sub.3 -phenyl                                                  59        4-CCl.sub.3 -phenyl                                                  60        2-NMe.sub.2 -phenyl                                                  61        3-NMe.sub.2 -phenyl                                                  62        4-NMe.sub.2 -phenyl                                                  63        2-tert.-butylphenyl                                                  64        3-tert.-butylphenyl                                                  65        4-tert.-butylphenyl                                                  66        2-tert.-butoxyphenyl                                                 67        3-tert.-butoxyphenyl                                                 68        4-tert.-butoxyphenyl                                                 69        2-phenylphenyl                                                       70        3-phenylphenyl                                                       71        4-phenylphenyl                                                       72        2-phenoxyphenyl                                                      73        3-phenoxyphenyl                                                      74        4-phenoxyphenyl                                                      75        1-napthyl                                                            76        2-napthyl                                                            77        2,3-Me.sub.2 -phenyl                                                 78        2,4-Me.sub.2 -phenyl                                                 79        2,5-Me.sub.2 -phenyl                                                 80        2,6-Me.sub.2 -phenyl                                                 81        3,4-Me.sub.2 -phenyl                                                 82        3,5-Me.sub.2 -phenyl                                                 83        2,4,6-Me.sub.3 -phenyl                                               84        2,3-Cl.sub.2 -phenyl                                                 85        2,4-Cl.sub.2 -phenyl                                                 86        2,5-Cl.sub.2 -phenyl                                                 87        2,6-Cl.sub.2 -phenyl                                                 88        3,4-Cl.sub.2 -phenyl                                                 89        3,5-Cl.sub.2 -phenyl                                                 90        2-pyridyl                                                            91        3-pyridyl                                                            92        4-pyridyl                                                            93        2-furyl                                                              94        3-furyl                                                              95        2-(5-NO.sub.2 -furyl)                                                96        2-thienyl                                                            97        2-(5-Cl-thienyl)                                                     98        2-(3-Cl-thienyl)                                                     99        3-(thienyl)                                                          100       2-benzofuranyl                                                       101       2-benzothienyl                                                       102       5-isoxazolyl                                                         103       3-(2-Cl-pyridyl)                                                     104       3-(6-Cl-pyridyl)                                                     105       4-(2,6-Cl.sub.2 -pyridyl)                                            106       3-(5,6-Cl.sub.2 -pyridyl)                                            107       3-(2-phenoxypyridyl)                                                 ______________________________________                                    

                  TABLE 6                                                          ______________________________________                                          ##STR27##                                                                                        phys. data                                                                     m. p.  °C.!                                                             IR  cm.sup.-1!                                              No.  R.sup.18      .sup.1 H-NMR  δ scale!                                ______________________________________                                         1    OH                                                                        2    O-methyl                                                                  3    O-ethyl                                                                   4    O-(n-propyl)                                                              5    O-(i-propyl)                                                              6    O-(n-butyl)                                                               7    O-(i-butyl)                                                               8    O-(s-butyl)                                                               9    O-(tert.-butyl)                                                           10   O-benzyl                                                                  11   O-(2-methylbenzyl)                                                        12   O-(3-methylbenzyl)                                                        13   O-(4-methylbenzyl)                                                        14   O-(2-Cl-benzyl)                                                           15   O-(3-Cl-benzyl)                                                           16   O-(4-Cl-benzyl)                                                           17   methyl                                                                    18   ethyl                                                                     19   n-propyl                                                                  20   i-propyl                                                                  21   n-butyl                                                                   22   i-butyl                                                                   23   s-butyl                                                                   24   tert.-butyl                                                               25   benzyl                                                                    26   phenyl        89-94° C.                                            27   2-Me-phenyl   95-98° C.                                            28   3-Me-phenyl   90-92° C.                                            29   4-Me-phenyl   103-112° C.                                          30   2-F-phenyl                                                                31   3-F-phenyl                                                                32   4-F-phenyl                                                                33   2-Cl-phenyl   88-93° C.                                            34   3-Cl-phenyl   97-102° C.                                           35   4-Cl-phenyl   3.87, 4.07 (OCH.sub.3), 7.35-8.11 ppm (8H).                 36   2-Br-phenyl                                                               37   3-Br-phenyl                                                               38   4-Br-phenyl   98-104° C.                                           39   2-I-phenyl                                                                40   3-I-phenyl                                                                41   4-I-phenyl                                                                42   2-CF.sub.3 -phenyl                                                                           2.82, 4.03 (OCH.sub.3), 7.34-8.11 ppm (8H).                 43   3-CF.sub.3 -phenyl                                                                           88-90° C.                                            44   4-CF.sub.3 -phenyl                                                                           3.87, 4.07 (OCH.sub.3), 7.35-8.28 ppm (8H).                 45   2-OCH.sub.3 -phenyl                                                       46   3-OCH.sub.3 -phenyl                                                       47   4-OCH.sub.3 -phenyl                                                       48   2-CN-phenyl                                                               49   3-CN-phenyl                                                               50   4-CN-phenyl                                                               51   2-NO.sub.2 -phenyl                                                        52   3-NO.sub.2 -phenyl                                                        53   4-NO.sub.2 -phenyl                                                        54   2-OCF.sub.3 -phenyl                                                       55   3-OCF.sub.3 -phenyl                                                       56   4-OCF.sub.3 -phenyl                                                       57   2-CCl.sub.3 -phenyl                                                       58   3-CCl.sub.3 -phenyl                                                       59   4-CCl.sub.3 -phenyl                                                       60   2-NMe.sub.2 -phenyl                                                       61   3-NMe.sub.2 -phenyl                                                       62   4-NMe.sub.2 -phenyl                                                       63   2-tert.-butylphenyl                                                       64   3-tert.-butylphenyl                                                       65   4-tert.-butylphenyl                                                       66   2-tert.-butoxyphenyl                                                      67   3-tert.-butoxyphenyl                                                      68   4-tert.-butoxyphenyl                                                      69   2-phenylphenyl                                                            70   3-phenylphenyl                                                            71   4-phenylphenyl                                                            72   2-phenoxyphenyl                                                           73   3-phenoxyphenyl                                                           74   4-phenoxyphenyl                                                           75   1-napthyl                                                                 76   2-napthyl                                                                 77   2,3-Me.sub.2 -phenyl                                                      78   2,4-Me.sub.2 -phenyl                                                      79   2,5-Me.sub.2 -phenyl                                                      80   2,6-Me.sub.2 -phenyl                                                      81   3,4-Me.sub.2 -phenyl                                                      82   3,5-Me.sub.2 -phenyl                                                      83   2,4,6-Me.sub.3 -phenyl                                                    84   2,3-Cl.sub.2 -phenyl                                                      85   2,4-Cl.sub.2 -phenyl                                                                         107-112° C.                                          86   2,5-Cl.sub.2 -phenyl                                                      87   2,6-Cl.sub.2 -phenyl                                                      88   3,4-Cl.sub.2 -phenyl                                                      89   3,5-Cl.sub.2 -phenyl                                                                         152-157° C.                                          90   2-pyridyl                                                                 91   3-pyridyl                                                                 92   4-pyridyl                                                                 93   2-furyl                                                                   94   3-furyl                                                                   95   2-(5-NO.sub.2 -furyl)                                                     96   2-thienyl                                                                 97   2-(5-Cl-thienyl)                                                          98   2-(3-Cl-thienyl)                                                          99   3-(thienyl)                                                               100  2-benzofuranyl                                                            101  2-benzothienyl                                                            102  5-isoxazolyl                                                              103  3-(2-Cl-pyridyl)                                                          104  3-(6-Cl-pyridyl)                                                          105  4-(2,6-Cl.sub.2 -pyridyl)                                                 106  3-(5,6-Cl.sub.2 -pyridyl)                                                 107  3-(2-phenoxypyridyl)                                                      ______________________________________                                    

                  TABLE 7                                                          ______________________________________                                          ##STR28##                                                                                               phys. data                                                                     m. p.  °C.!                                                             IR  cm.sup.-1!                                       No.       R.sup.18        .sup.1 H-NMR  δ scale!                         ______________________________________                                         1         OH                                                                   2         O-methyl                                                             3         O-ethyl                                                              4         O-(n-propyl)                                                         5         O-(i-propyl)                                                         6         O-(n-butyl)                                                          7         O-(i-butyl)                                                          8         O-(s-butyl)                                                          9         O-(tert.-butyl)                                                      10        O-benzyl                                                             11        O-(2-methylbenzyl)                                                   12        O-(3-methylbenzyl)                                                   13        O-(4-methylbenzyl)                                                   14        O-(2-Cl-benzyl)                                                      15        O-(3-Cl-benzyl)                                                      16        O-(4-Cl-benzyl)                                                      17        methyl                                                               18        ethyl                                                                19        n-propyl                                                             20        i-propyl                                                             21        n-butyl                                                              22        i-butyl                                                              23        s-butyl                                                              24        tert.-butyl                                                          25        benzyl                                                               26        phenyl                                                               27        2-Me-phenyl                                                          28        3-Me-phenyl                                                          29        4-Me-phenyl                                                          30        2-F-phenyl                                                           31        3-F-phenyl                                                           32        4-F-phenyl                                                           33        2-Cl-phenyl                                                          34        3-Cl-phenyl                                                          35        4-Cl-phenyl                                                          36        2-Br-phenyl                                                          37        3-Br-phenyl                                                          38        4-Br-phenyl                                                          39        2-I-phenyl                                                           40        3-I-phenyl                                                           41        4-I-phenyl                                                           42        2-CF.sub.3 -phenyl                                                   43        3-CF.sub.3 -phenyl                                                   44        4-CF.sub.3 -phenyl                                                   45        2-OCH.sub.3 -phenyl                                                  46        3-OCH.sub.3 -phenyl                                                  47        4-OCH.sub.3 -phenyl                                                  48        2-CN-phenyl                                                          49        3-CN-phenyl                                                          50        4-CN-phenyl                                                          51        2-NO.sub.2 -phenyl                                                   52        3-NO.sub.2 -phenyl                                                   53        4-NO.sub.2 -phenyl                                                   54        2-OCF.sub.3 -phenyl                                                  55        3-OCF.sub.3 -phenyl                                                  56        4-OCF.sub.3 -phenyl                                                  57        2-CCl.sub.3 -phenyl                                                  58        3-CCl.sub.3 -phenyl                                                  59        4-CCl.sub.3 -phenyl                                                  60        2-NMe.sub.2 -phenyl                                                  61        3-NMe.sub.2 -phenyl                                                  62        4-NMe.sub.2 -phenyl                                                  63        2-tert.-butylphenyl                                                  64        3-tert.-butylphenyl                                                  65        4-tert.-butylphenyl                                                  66        2-tert.-butoxyphenyl                                                 67        3-tert.-butoxyphenyl                                                 68        4-tert.-butoxyphenyl                                                 69        2-phenylphenyl                                                       70        3-phenylphenyl                                                       71        4-phenylphenyl                                                       72        2-phenoxyphenyl                                                      73        3-phenoxyphenyl                                                      74        4-phenoxyphenyl                                                      75        1-napthyl                                                            76        2-napthyl                                                            77        2,3-Me.sub.2 -phenyl                                                 78        2,4-Me.sub.2 -phenyl                                                 79        2,5-Me.sub.2 -phenyl                                                 80        2,6-Me.sub.2 -phenyl                                                 81        3,4-Me.sub.2 -phenyl                                                 82        3,5-Me.sub.2 -phenyl                                                 83        2,4,6-Me.sub.3 -phenyl                                               84        2,3-Cl.sub.2 -phenyl                                                 85        2,4-Cl.sub.2 -phenyl                                                 86        2,5-Cl.sub.2 -phenyl                                                 87        2,6-Cl.sub.2 -phenyl                                                 88        3,4-Cl.sub.2 -phenyl                                                 89        3,5-Cl.sub.2 -phenyl                                                 90        2-pyridyl                                                            91        3-pyridyl                                                            92        4-pyridyl                                                            93        2-furyl                                                              94        3-furyl                                                              95        2-(5-NO.sub.2 -furyl)                                                96        2-thienyl                                                            97        2-(5-Cl-thienyl)                                                     98        2-(3-Cl-thienyl)                                                     99        3-(thienyl)                                                          100       2-benzofuranyl                                                       101       2-benzothienyl                                                       102       5-isoxazolyl                                                         103       3-(2-Cl-pyridyl)                                                     104       3-(6-Cl-pyridyl)                                                     105       4-(2,6-Cl.sub.2 -pyridyl)                                            106       3-(5,6-Cl.sub.2 -pyridyl)                                            107       3-(2-phenoxypyridyl)                                                 ______________________________________                                    

                  TABLE 8                                                          ______________________________________                                          ##STR29##                                                                                               phys. data                                                                     m. p.  °C.!                                                             IR  cm.sup.-1!                                       No.       R.sup.18        .sup.1 H-NMR  δ scale!                         ______________________________________                                         1         OH                                                                   2         O-methyl                                                             3         O-ethyl                                                              4         O-(n-propyl)                                                         5         O-(i-propyl)                                                         6         O-(n-butyl)                                                          7         O-(i-butyl)                                                          8         O-(s-butyl)                                                          9         O-(tert.-butyl)                                                      10        O-benzyl                                                             11        O-(2-methylbenzyl)                                                   12        O-(3-methylbenzyl)                                                   13        O-(4-methylbenzyl)                                                   14        O-(2-Cl-benzyl)                                                      15        O-(3-Cl-benzyl)                                                      16        O-(4-Cl-benzyl)                                                      17        methyl                                                               18        ethyl                                                                19        n-propyl                                                             20        i-propyl                                                             21        n-butyl                                                              22        i-butyl                                                              23        s-butyl                                                              24        tert.-butyl                                                          25        benzyl                                                               26        phenyl                                                               27        2-Me-phenyl                                                          28        3-Me-phenyl                                                          29        4-Me-phenyl                                                          30        2-F-phenyl                                                           31        3-F-phenyl                                                           32        4-F-phenyl                                                           33        2-Cl-phenyl                                                          34        3-Cl-phenyl                                                          35        4-Cl-phenyl                                                          36        2-Br-phenyl                                                          37        3-Br-phenyl                                                          38        4-Br-phenyl                                                          39        2-I-phenyl                                                           40        3-I-phenyl                                                           41        4-I-phenyl                                                           42        2-CF.sub.3 -phenyl                                                   43        3-CF.sub.3 -phenyl                                                   44        4-CF.sub.3 -phenyl                                                   45        2-OCH.sub.3 -phenyl                                                  46        3-OCH.sub.3 -phenyl                                                  47        4-OCH.sub.3 -phenyl                                                  48        2-CN-phenyl                                                          49        3-CN-phenyl                                                          50        4-CN-phenyl                                                          51        2-NO.sub.2 -phenyl                                                   52        3-NO.sub.2 -phenyl                                                   53        4-NO.sub.2 -phenyl                                                   54        2-OCF.sub.3 -phenyl                                                  55        3-OCF.sub.3 -phenyl                                                  56        4-OCF.sub.3 -phenyl                                                  57        2-CCl.sub.3 -phenyl                                                  58        3-CCl.sub.3 -phenyl                                                  59        4-CCl.sub.3 -phenyl                                                  60        2-NMe.sub.2 -phenyl                                                  61        3-NMe.sub.2 -phenyl                                                  62        4-NMe.sub.2 -phenyl                                                  63        2-tert.-butylphenyl                                                  64        3-tert.-butylphenyl                                                  65        4-tert.-butylphenyl                                                  66        2-tert.-butoxyphenyl                                                 67        3-tert.-butoxyphenyl                                                 68        4-tert.-butoxyphenyl                                                 69        2-phenylphenyl                                                       70        3-phenylphenyl                                                       71        4-phenylphenyl                                                       72        2-phenoxyphenyl                                                      73        3-phenoxyphenyl                                                      74        4-phenoxyphenyl                                                      75        1-napthyl                                                            76        2-napthyl                                                            77        2,3-Me.sub.2 -phenyl                                                 78        2,4-Me.sub.2 -phenyl                                                 79        2,5-Me.sub.2 -phenyl                                                 80        2,6-Me.sub.2 -phenyl                                                 81        3,4-Me.sub.2 -phenyl                                                 82        3,5-Me.sub.2 -phenyl                                                 83        2,4,6-Me.sub.3 -phenyl                                               84        2,3-Cl.sub.2 -phenyl                                                 85        2,4-Cl.sub.2 -phenyl                                                 86        2,5-Cl.sub.2 -phenyl                                                 87        2,6-Cl.sub.2 -phenyl                                                 88        3,4-Cl.sub.2 -phenyl                                                 89        3,5-Cl.sub.2 -phenyl                                                 90        2-pyridyl                                                            91        3-pyridyl                                                            92        4-pyridyl                                                            93        2-furyl                                                              94        3-furyl                                                              95        2-(5-NO.sub.2 -furyl)                                                96        2-thienyl                                                            97        2-(5-Cl-thienyl)                                                     98        2-(3-Cl-thienyl)                                                     99        3-(thienyl)                                                          100       2-benzofuranyl                                                       101       2-benzothienyl                                                       102       5-isoxazolyl                                                         103       3-(2-Cl-pyridyl)                                                     104       3-(6-Cl-pyridyl)                                                     105       4-(2,6-Cl.sub.2 -pyridyl)                                            106       3-(5,6-Cl.sub.2 -pyridyl)                                            107       3-(2-phenoxypyridyl)                                                 ______________________________________                                    

                  TABLE 9                                                          ______________________________________                                          ##STR30##                                                                                            phys. data                                                                     m. p.  °C.!                                                             IR  cm.sup.-1!                                          No.     R.sup.20       .sup.1 H-NMR  δ scale!                            ______________________________________                                         1       methyl                                                                 2       ethyl                                                                  3       n-propyl                                                               4       i-propyl                                                               5       n-butyl                                                                6       i-butyl                                                                7       s-butyl                                                                8       tert.-butyl                                                            9       benzyl                                                                 10      phenyl         3.81; 4.04; 4.12 (CH.sub.3);                                                   7.28-7.88 ppm (9H)                                      11      2-Me-phenyl                                                            12      3-Me-phenyl    2.42; 3.81, 4.05; 4.12 (CH.sub.3);                                             7.17-7.71 ppm (8H).                                     13      4-Me-phenyl    2.38; 3.82; 4.05; 4.11 (CH.sub.3);                                             7.18-7.75 ppm (8H).                                     14      2-F-phenyl                                                             15      3-F-phenyl                                                             16      4-F-phenyl                                                             17      2-Cl-phenyl    3.76; 4.00; 4.12 (CH.sub.3);                                                   7.28-7.61 ppm (8H).                                     18      3-Cl-phenyl                                                            19      4-Cl-phenyl                                                            20      2-Br-phenyl                                                            21      3-Br-phenyl                                                            22      4-Br-phenyl                                                            23      2-I-phenyl                                                             24      3-I-phenyl                                                             25      4-I-phenyl                                                             26      2-CF.sub.3 -phenyl                                                     27      3-CF.sub.3 -phenyl                                                                            3.81; 4.05; 4.15 (CH.sub.3);                                                   7.28-8.11 ppm (8H).                                     28      4-CF.sub.3 -phenyl                                                                            3.82; 4.05; 4.15 (CH.sub.3);                                                   7.30-7.98 ppm (8H).                                     29      2-OCH.sub.3 -phenyl                                                    30      3-OCH.sub.3 -phenyl                                                    31      4-OCH.sub.3 -phenyl                                                    32      2-CN-phenyl                                                            33      3-CN-phenyl                                                            34      4-CN-phenyl                                                            35      2-NO.sub.2 -phenyl                                                     36      3-NO.sub.2 -phenyl                                                     37      4-NO.sub.2 -phenyl                                                     38      2-OCF.sub.3 -phenyl                                                    39      3-OCF.sub.3 -phenyl                                                    40      4-OCF.sub.3 -phenyl                                                    41      2-CCl.sub.3 -phenyl                                                    42      3-CCl.sub.3 -phenyl                                                    43      4-CCl.sub.3 -phenyl                                                    44      2-NMe.sub.2 -phenyl                                                    45      3-NMe.sub.2 -phenyl                                                    46      4-NMe.sub.2 -phenyl                                                    47      2-tert.-butylphenyl                                                    48      3-tert.-butylphenyl                                                    49      4-tert.-butylphenyl                                                    50      2-tert.-butoxyphenyl                                                   51      3-tert.-butoxyphenyl                                                   52      4-tert.-butoxyphenyl                                                   53      2-phenylphenyl                                                         54      3-phenylphenyl                                                         55      4-phenylphenyl                                                         56      2-phenoxyphenyl                                                        57      3-phenoxyphenyl                                                        58      4-phenoxyphenyl                                                        59      1-napthyl                                                              60      2-napthyl                                                              61      2,3-Me.sub.2 -phenyl                                                   62      2,4-Me.sub.2 -phenyl                                                   63      2,5-Me.sub.2 -phenyl                                                   64      2,6-Me.sub.2 -phenyl                                                   65      3,4-Me.sub.2 -phenyl                                                   66      3,5-Me.sub.2 -phenyl                                                   67      2,4,6-Me.sub.3 -phenyl                                                 68      2,3-Cl.sub.2 -phenyl                                                   69      2,4-Cl.sub.2 -phenyl                                                   70      2,5-Cl.sub.2 -phenyl                                                   71      2,6-Cl.sub.2 -phenyl                                                   72      3,4-Cl.sub.2 -phenyl                                                   73      3,5-Cl.sub.2 -phenyl                                                   74      2-pyridyl                                                              75      3-pyridyl                                                              76      4-pyridyl                                                              77      2-furyl                                                                78      3-furyl                                                                79      2-(5-NO.sub.2 -furyl)                                                  80      2-thienyl                                                              81      2-(5-Cl-thienyl)                                                       82      2-(3-Cl-thienyl)                                                       83      3-(thienyl)                                                            84      2-benzofuranyl                                                         85      2-benzothienyl                                                         86      5-isoxazolyl                                                           87      3-(2-Cl-pyridyl)                                                       88      3-(6-Cl-pyridyl)                                                       89      4-(2,6-Cl.sub.2 -pyridyl)                                              90      3-(5,6-Cl.sub.2 -pyridyl)                                              91      3-(2-phenoxypyridyl)                                                   ______________________________________                                    

                  TABLE 10                                                         ______________________________________                                          ##STR31##                                                                                              phys. data                                                                     m.p.  °C.!                                                              IR  cm.sup.-1 !                                       No.      R.sup.20        .sup.1 H-NMR  δ scale!                          ______________________________________                                         1        methyl                                                                2        ethyl                                                                 3        n-propyl                                                              4        i-propyl                                                              5        n-butyl                                                               6        i-butyl                                                               7        s-butyl                                                               8        tert.-butyl                                                           9        benzyl                                                                10       phenyl          2.85(d, 3H); 3.94; 4.10                                                        (CH.sub.3); 6.79(NH), 7.28-                                                    7.84 ppm(9H)                                          11       2-Me-phenyl                                                           12       3-Me-phenyl                                                           13       4-Me-phenyl                                                           14       2-F-phenyl                                                            15       3-F-phenyl                                                            16       4-F-phenyl                                                            17       2-Cl-phenyl                                                           18       3-Cl-phenyl                                                           19       4-Cl-phenyl                                                           20       2-Br-phenyl                                                           21       3-Br-phenyl                                                           22       4-Br-phenyl                                                           23       2-I-phenyl                                                            24       3-I-phenyl                                                            25       4-I-phenyl                                                            26       2-CF.sub.3 -phenyl                                                    27       3-CF.sub.3 -phenyl                                                    28       4-CF.sub.3 -phenyl                                                    29       2-OCH.sub.3 -phenyl                                                   30       3-OCH.sub.3 -phenyl                                                   31       4-OCH.sub.3 -phenyl                                                   32       2-CN-phenyl                                                           33       3-CN-phenyl                                                           34       4-CN-phenyl                                                           35       2-NO.sub.2 -phenyl                                                    36       3-NO.sub.2 -phenyl                                                    37       4-NO.sub.2 -phenyl                                                    38       2-OCF.sub.3 -phenyl                                                   39       3-OCF.sub.3 -phenyl                                                   40       4-OCF.sub.3 -phenyl                                                   41       2-CCl.sub.3 -phenyl                                                   42       3-CCl.sub.3 -phenyl                                                   43       4-CCl.sub.3 -phenyl                                                   44       2-NMe.sub.2 -phenyl                                                   45       3-NMe.sub.2 -phenyl                                                   46       4-NMe.sub.2 -phenyl                                                   47       2-tert.-butylphenyl                                                   48       3-tert.-butylphenyl                                                   49       4-tert.-butylphenyl                                                   50       2-tert.-butoxyphenyl                                                  51       3-tert.-butoxyphenyl                                                  52       4-tert.-butoxyphenyl                                                  53       2-phenylphenyl                                                        54       3-phenylphenyl                                                        55       4-phenylphenyl                                                        56       2-phenoxyphenyl                                                       57       3-phenoxyphenyl                                                       58       4-phenoxyphenyl                                                       59       1-naphthyl                                                            60       2-naphthyl                                                            61       2,3-Me.sub.2 -phenyl                                                  62       2,4-Me.sub.2 -phenyl                                                  63       2,5-Me.sub.2 -phenyl                                                  64       2,6-Me.sub.2 -phenyl                                                  65       3,4-Me.sub.2 -phenyl                                                  66       3,5-Me.sub.2 -phenyl                                                  67       2,4,6-Me.sub.3 -phenyl                                                68       2,3-Cl.sub.2 -phenyl                                                  69       2,4-Cl.sub.2 -phenyl                                                  70       2,5-Cl.sub.2 -phenyl                                                  71       2,6-Cl.sub.2 -phenyl                                                  72       3,4-Cl.sub.2 -phenyl                                                  73       3,5-Cl.sub.2 -phenyl                                                  74       2-pyridyl                                                             75       3-pyridyl                                                             76       4-pyridyl                                                             77       2-furyl                                                               78       3-furyl                                                               79       2-(5-NO.sub.2 -furyl)                                                 80       2-thienyl                                                             81       2-(5-Cl-thienyl)                                                      82       2-(3-Cl-thienyl)                                                      83       3-(thienyl)                                                           84       2-benzofuranyl                                                        85       2-benzothienyl                                                        86       5-isoxazolyl                                                          87       3-(2-Cl-pyridyl)                                                      88       3-(6-Cl-pyridyl)                                                      89       4-(2,6-Cl.sub.2 -pyridyl)                                             90       3-(5,6-Cl.sub.2 -pyridyl)                                             91       3-(2-phenoxypyridyl)                                                  ______________________________________                                    

The novel compounds are suitable as fungicides.

The fungicidal compounds according to the invention, or agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

Normally, the plants are sprayed or dusted with the active ingredients or the seeds of the plants are treated with the active ingredients.

The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin-sulfite waste liquors and methylcellulose.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyelene, octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributulphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

Examples of such formulations are given below.

I. A solution of 90 parts by weight of compound no. 1 from Table 2 and 10 parts by weight of N-methyl-α-pyrrolidone, which is suitable for application in the form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 24 from Table 2, 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely dispersing the mixture in water, a dispersion is obtained.

III. An aqueous dispersion of 20 parts by weight of compound no. 25 from Table 2, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

IV. An aqueous dispersion of 20 parts by weight of compound no. 26 from Table 2, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

V. A hammer-milled mixture of 80 parts by weight of compound no. 31 from Table 2, 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel. By finely dispersing the mixture in water, a spray liquor is obtained.

VI. An intimate mixture of 3 parts by weight of compound no. 33 from Table 2 and 97 parts by weight of particulate kaolin. The dust contains 3 wt % of the active ingredient.

VII. An intimate mixture of 30 parts by weight of compound no. 34 from Table 2, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. This formulation of the active ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound no. 35 from Table 2, 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water, which dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound no. 42 from Table 2, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.

The novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a remarkably high systemic mobility and action after application to the soil and particularly to foliage.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The compounds are applied by treating the seeds, plants, materials or soil to be protected against fungus attack with a fungicidally effective amount of the active ingredients.

The compounds may be applied before or after infection of the materials, plants or seeds by the fungi.

The compounds I are particularly useful for controlling the following plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia solani in cotton,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The novel compounds may also be used for protecting materials (timber), for example against Paecilomyces variotii.

The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt % of active ingredient.

The application rates depend on the type of effect desired, but are generally from 0.02 to 3 kg of active ingredient per hectare. when the active ingredients are used for treating seed, application rates of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are generally required.

When the agents according to the invention are used as fungicides, they may be employed together with other active ingredients, e.g., herbicides, insecticides, growth regulators, other fungicides and fertilizers.

When admixed with other fungicides, the spectrum of fungicidal action is in many instances increased.

Use Examples

In the active ingredients used for comparison purposes, U, V and W=H, A=CH₃ ON═, B=CH₃ O and R=phenyl (compound 1), R=2-chlorophenyl (compound B), and R=4-CF₃ -phenyl (compound C). All of these compounds are known from EP 253 213.

Use Example 1

Action on cucumber mildew

Young cucumber plants of the "Chinesische Schlange" variety were sprayed to runoff at the two-leaf stage with an aqueous spray liquor. The next day these plants were sprayed with an aqueous conidial suspension of cucumber mildew (Erysiphe cichoracearum and Sphaerotheca fuliginea), and kept in the greenhouse at 20 to 22° C. and a relative humidity of 70 to 80%. The extent of fungus spread was determined 21 days after application of the active ingredients.

The results show that the active ingredients from Table 2, no. 33 (2,33), 2,43; 2,148 and 2,166 have, when applied as a spray liquor containing 63 ppm of active ingredient, a better fungicidal action (10% leaf attack) than prior art comparative active ingredients A, B and C (45% leaf attack).

Use Example 2

Action on Botrytis cinerea in paprika pods (fruit test)

Slices of green paprika pods were sprayed to runoff with aqueous formulations containing 80% of active ingredient and 20% of emulsifier. Two hours after the sprayed-on layer had dried, the slices were inoculated with a spore suspension of Botrytis cinerea containing 1.7×10⁶ spores per ml of a 2% biomalt solution. The inoculated slices were then incubated in moist chambers for 4 days at 18° C. The extent of Botrytis spread on the slices was then assessed visually.

The results show that active ingredients 2,25; 2,35; 2,166 and 2,179, when applied as spray liquors containing 500 ppm of active ingredient, have a better fungicidal action (10% attack) than prior art comparative active ingredient A (30% attack).

Use Example 3

Action on Plasmopara Viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 48 hours in a water vapor-saturated chamber at 24° C. and then in a greenhouse for 5 days at from 20° to 30° C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.

The results show that active ingredients 1,195; 2,25; 2,35; 2,43; 2,86; 2,88; 2,92; 2,94; 2,95 and 2,148, when applied as spray liquors containing 16 ppm of active ingredient, have a better fungicidal action (5% leaf attack) than prior art comparative active ingredient C (35% leaf attack). 

We claim:
 1. An acetylene derivative of the formula I ##STR32## where U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,A is C₁ -C₄ -alkylidene, C₁ -C₄ -alkoxymethylidene, C₁ -C₄ -alkylthiomethylidene or C₁ -C₄ -alkoximino, B is OH, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino and R is unsubstituted or substituted hetaryl selected from the group consisting of pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3-furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl and 2-benzothiazolyl, the term "unsubstituted or substituted" denoting, in addition to hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy, benzyl, benzyloxy, hetaryl, hetaryloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄ -dialkylamino, CO₂ Me, CO₂ Et, formyl or acyl, Me is methyl and Et is ethyl, and the term "hetaryl" denoting an aromatic five-membered or six-membered heterocyclic structure.
 2. An acetylene derivative of the formula II ##STR33## where R is as defined in claim
 1. 3. An acetylene derivative of the formula IV ##STR34## where R is as defined in claim
 1. 4. An acetylene derivative of the formula V ##STR35## where R is as defined in claim
 1. 5. An acetylene derivative of the formula VI ##STR36## where R is as defined in claim
 1. 6. A fungicide containing an inert carrier and a fungicidally effective amount of an acetylene derivative of the formula I ##STR37## where U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,A is C₁ -C₄ -alkylidene, C₁ -C₄ -alkoxymethylidene, C₁ -C₄ -alkylthiomethylidene or C₁ -C₄ -alkoximino, B is OH, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino and R is unsubstituted or substituted hetaryl selected from the group consisting of pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol -5-yl, 1,3,4-thiadiazol-2-yl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl and 2-benzothiazolyl, the term "unsubstituted or substituted" denoting, in addition to hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy, benzyl, benzyloxy, hetaryl, hetaryloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄ -dialkylamino, CO₂ Me, CO₂ Et, formyl or acyl, Me is methyl and Et is ethyl, and the term "hetaryl" denoting an aromatic five-membered or six-membered heterocyclic structure.
 7. A method of combating fungi, wherein the fungi, or the materials, plants or seeds to be protected against fungus attack, or the soil are treated with a fungicidally effective amount of a compound of the formula ##STR38## where U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,A is C₁ -C₄ -alkylidene, C₁ -C₄ -alkoxymethylidene, C₁ -C₄ -alkylthiomethylidene or C₁ -C₄ -alkoximino, B is OH, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino and R is unsubstituted or substituted hetaryl selected from the group consisting of pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3-furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl and 2-benzothiazolyl, the term "unsubstituted or substituted" denoting, in addition to hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy, benzyl, benzyloxy, hetaryl, hetaryloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄ -dialkylamino, CO₂ Me, CO₂ Et, formyl or acyl, Me is methyl and Et is ethyl, and the term "hetaryl" denoting an aromatic five-membered or six-membered heterocyclic structure.
 8. A method of combating insects, nematodes and mites, wherein the insects, nematodes or mites, or the place where they are located, are treated with an effective amount of a compound of the formula I ##STR39## where U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,A is C₁ -C₄ -alkylidene, C₁ -C₄ -alkoxymethylidene, C₁ -C₄ -alkylthiomethylidene or C₁ -C₄ -alkoximino, B is OH, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino and R is unsubstituted or substituted hetaryl selected from the group consisting of pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3-furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl and 2-benzothiazolyl, the term "unsubstituted or substituted" denoting, in addition to hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy, benzyl, benzyloxy, hetaryl, hetaryloxy, C₃ -C₆ -cycloalkyl , C₁ -C₄ -dialkylamino, CO₂ Me, CO₂ Et, formyl or acyl, Me is methyl and Et is ethyl, and the term "hetaryl" denoting an aromatic five-membered or six-membered heterocyclic structure.
 9. The acetylene derivative of claim 1, wherein A is C₁ -C₄ -alkylidene.
 10. The acetylene derivative of claim 1, wherein A is C₁ -C₄ -alkoxymethylidene.
 11. The acetylene derivative of claim 1, wherein A is C₁ -C₄ -alkylthiomethylidene.
 12. The acetylene derivative of claim 1, wherein A is C₁ -C₄ -alkoximino.
 13. An acetylene derivative of the formula I ##STR40## where U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,A is C₁ -C₄ -alkylidene, C₁ -C₄ -alkoxymethylidene, C₁ -C₄ -alkylthiomethylidene or C₁ -C₄ -alkoximino, B is OH, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino and R is unsubstituted or substituted hetaryl selected from the group consisting of pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3-furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl and 2-benzothiazolyl, the term "unsubstituted or substituted" denoting, in addition to hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy, benzyl, benzyloxy, hetaryl, hetaryloxy, C₃ -C₆ -cycloalkyl, C₁ -C₄ -dialkylamino, CO₂ Me, CO₂ Et, formyl or acyl, Me is methyl and Et is ethyl, and the term "hetaryl" denoting an aromatic five-membered or six-membered heterocyclic structure.
 14. A method of combatting fungi, wherein the fungi, or the materials, plants or seeds to be protected against fungus attack, or the soil are treated with a fungicidally effective amount of the compound of claim
 13. 15. A method of combatting insects, nematodes and mites, wherein the insects, nematodes or mites, or the place where they are located, are treated with an effective amount of the compound of claim
 13. 16. The acetylene derivative of claim 1, wherein A is C₁ -C₄ -alkoximino and R is unsubstituted or substituted hetaryl selected from the group consisting of pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3-furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl and 2-benzothiazolyl.
 17. The acetylene derivative of claim 16, which is methyl 2-(4-(2-chloro)thienylethynyl)phenylglyoxylate O-methyloxime.
 18. The acetylene derivative of claim 1, wherein A is NOCH₃ and B is OCH₃. 